CN102627885A - Ink set and image forming method - Google Patents
Ink set and image forming method Download PDFInfo
- Publication number
- CN102627885A CN102627885A CN2012100202593A CN201210020259A CN102627885A CN 102627885 A CN102627885 A CN 102627885A CN 2012100202593 A CN2012100202593 A CN 2012100202593A CN 201210020259 A CN201210020259 A CN 201210020259A CN 102627885 A CN102627885 A CN 102627885A
- Authority
- CN
- China
- Prior art keywords
- ink
- pigment
- quality
- yellow
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 235000019259 sodium dehydroacetate Nutrition 0.000 description 1
- 229940079839 sodium dehydroacetate Drugs 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- LROWVYNUWKVTCU-STWYSWDKSA-M sodium sorbate Chemical compound [Na+].C\C=C\C=C\C([O-])=O LROWVYNUWKVTCU-STWYSWDKSA-M 0.000 description 1
- 235000019250 sodium sorbate Nutrition 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- DSOWAKKSGYUMTF-GZOLSCHFSA-M sodium;(1e)-1-(6-methyl-2,4-dioxopyran-3-ylidene)ethanolate Chemical compound [Na+].C\C([O-])=C1/C(=O)OC(C)=CC1=O DSOWAKKSGYUMTF-GZOLSCHFSA-M 0.000 description 1
- HCJLVWUMMKIQIM-UHFFFAOYSA-M sodium;2,3,4,5,6-pentachlorophenolate Chemical compound [Na+].[O-]C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl HCJLVWUMMKIQIM-UHFFFAOYSA-M 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-N sodium;acetic acid Chemical compound [Na+].CC(O)=O VMHLLURERBWHNL-UHFFFAOYSA-N 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- QERYCTSHXKAMIS-UHFFFAOYSA-N thiophene-2-carboxylic acid Chemical compound OC(=O)C1=CC=CS1 QERYCTSHXKAMIS-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0011—Pre-treatment or treatment during printing of the recording material, e.g. heating, irradiating
- B41M5/0017—Application of ink-fixing material, e.g. mordant, precipitating agent, on the substrate prior to printing, e.g. by ink-jet printing, coating or spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/21—Ink jet for multi-colour printing
- B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/21—Ink jet for multi-colour printing
- B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
- B41J2/2114—Ejecting specialized liquids, e.g. transparent or processing liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/0081—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using electromagnetic radiation or waves, e.g. ultraviolet radiation, electron beams
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/322—Pigment inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
- C09D11/326—Inkjet printing inks characterised by colouring agents containing carbon black characterised by the pigment dispersant
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Electromagnetism (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ink Jet Recording Methods And Recording Media Thereof (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ink Jet (AREA)
Abstract
An ink set is disclosed which includes a yellow ink composition containing a resin-coated yellow pigment in which a yellow pigment is coated with a crosslinked water-soluble resin, a water-soluble polymerizable compound and water; a magenta ink composition containing a resin-coated magenta pigment in which a magenta pigment is coated with a crosslinked water-soluble resin, a water-soluble polymerizable compound and water; a cyan ink composition containing a resin-coated cyan pigment in which a cyan pigment is coated with a crosslinked water-soluble resin, a water-soluble polymerizable compound and water; and a treatment liquid containing an aggregating agent for aggregating components in the ink compositions.
Description
Technical field
The present invention relates to printing ink group and formation method.
Background technology
Ink-jet technology has been used as the image recording process that record color image is used in fields such as office printer, household printer.
In ink-jet technology, the printing ink group that can use the printing ink that contains coloured material and other liquid combination to obtain.As the example; The known printing ink group that has the negatively charged ion that contains coloured material or cationic printing ink and liquid compsn combination to obtain; Wherein said liquid compsn contains the opposite polarity discrete particles of its surface polarity and printing ink; And contain the polymerizable components that when being applied in energy, can be solidified into polymkeric substance and can be with said polymerizable components dissolved solvent (for example, referring to open (JP-A) No.2002-332433 of Japanese patent application).
In addition, as employed printing ink group in the ink-jet technology, the also known printing ink group (for example, referring to Japanese documentation JP-A No.2003-160751,2007-161850 and 2009-149805) that has wherein the ink combination with two or more colors obtain.
Summary of the invention
Yet; About Japanese documentation JP-A No.2002-332433,2003-160751,2007-161850 and 2009-149805 disclosed ink composite in each; The erasibility that has been found that imaging and image maybe be not enough; Perhaps when being selected from any two kinds of colors in Yellow ink compsn, magenta ink compositions and the cyan ink composition through stack and forming redness, green or blue image, the colorrendering quality of red, blueness or green image maybe be not enough.
The present invention in view of the above problem and carry out; And the purpose of this invention is to provide a kind of printing ink group and formation method; They are being excellent aspect the erasibility of imaging and image, and also are being excellent aspect the colorrendering quality of redness, blueness or green image.
According to a first aspect of the invention, disclose a kind of printing ink group, having comprised: the Yellow ink compsn, it contains resin-coated yellow ultramarine, water-soluble polymerizable compound and the water of the water soluble resin lining that yellow ultramarine wherein is crosslinked; Magenta ink compositions, it contains resin-coated magenta pigment, water-soluble polymerizable compound and the water of the water soluble resin lining that magenta pigment wherein is crosslinked; Cyan ink composition, it contains resin-coated green pigment, water-soluble polymerizable compound and the water of the water soluble resin lining that green pigment wherein is crosslinked; And treatment solution, it contains the composition agglutinative agglutinant that makes in the ink composite.
Wherein, When any two kinds of ink composites when be selected from the group of being made up of said Yellow ink compsn, magenta ink compositions and cyan ink composition through stack in form redness, green or blue image, below satisfying, Yellow ink compsn, magenta ink compsn or the cyan ink composition that is at first sprayed in the middle of these two kinds of ink composites require one in (1) to (3):
(1) when the ink composite that is at first sprayed in the middle of said two kinds of ink composites is magenta ink compositions; The content of the magenta pigment in this magenta ink compositions is 4.2 quality % to 6.0 quality % with respect to the total amount of said magenta ink compositions, and said crosslinked water soluble resin and the mass ratio (quality of the quality/magenta pigment of crosslinked water soluble resin) of said magenta pigment are 0.25 or bigger;
(2) when the ink composite that is at first sprayed in the middle of said two kinds of ink composites is cyan ink composition; The content of the green pigment in this cyan ink composition is 2.0 quality % to 4.0 quality % with respect to the total amount of said cyan ink composition, and said crosslinked water soluble resin and the mass ratio (quality of the quality/green pigment of crosslinked water soluble resin) of said green pigment are 0.40 or bigger; Perhaps
(3) when the ink composite that is at first sprayed in the middle of said two kinds of ink composites is the Yellow ink compsn; The content of the yellow ultramarine in this Yellow ink compsn is 3.0 quality % to 6.0 quality % with respect to the total amount of said Yellow ink compsn, and said crosslinked water soluble resin and the mass ratio (quality of the quality/yellow ultramarine of crosslinked water soluble resin) of yellow ultramarine are 0.40 or bigger.
According to a second aspect of the invention, disclose a kind of formation method that uses the described printing ink group of first aspect, said method comprises:
The treatment solution that will contain the composition agglutinative agglutinant that makes in the ink composite is applied on the recording medium,
First ink composite that will be selected from said printing ink group through ink ejecting method is applied on the recording medium that has been applied with said treatment solution on it,
Second ink composite that will be selected from said printing ink group through ink ejecting method is applied on said first ink composite that is applied on the said recording medium, and
Thereby through to the recording medium that is applied with said ink composite, said ink composite being solidified the active-energy radiation irradiation.
The present invention can provide and demonstrate excellent imaging characteristic and image erasibility and tool
Printing ink group and formation method that the colorrendering quality of excellent redness, blueness or green image is arranged.
Brief Description Of Drawings
Fig. 1 is the synoptic diagram that is illustrated in the instance of the ink-jet recording device that uses in the formation method of the present invention.
Embodiment
< printing ink group >
Printing ink group according to the present invention comprises: the Yellow ink compsn, and it contains resin-coated yellow ultramarine, water-soluble polymerizable compound and the water of the water soluble resin lining that yellow ultramarine wherein is crosslinked; Magenta ink compositions, it contains resin-coated magenta pigment, water-soluble polymerizable compound and the water of the water soluble resin lining that magenta pigment wherein is crosslinked; Cyan ink composition, it contains resin-coated green pigment, water-soluble polymerizable compound and the water of the water soluble resin lining that green pigment wherein is crosslinked; And treatment solution; It contains and is useful on the composition agglutinative agglutinant that makes in the ink composite; Wherein, When any two kinds of ink composites when be selected from the group of being made up of said Yellow ink compsn, magenta ink compositions and cyan ink composition through stack in form redness, green or blue image, one in the requirement (1) to (3) that Yellow ink compsn, magenta ink compositions or the cyan ink composition that is at first sprayed in the middle of these two kinds of ink composites provides below satisfying.
(1) when the ink composite that is at first sprayed in the middle of two kinds of ink composites is magenta ink compositions; The content of the magenta pigment in this magenta ink compositions is 4.2 quality % to 6.0 quality % with respect to the total amount of said magenta ink compositions, and the mass ratio of crosslinked water soluble resin and magenta pigment (quality of the quality/magenta pigment of crosslinked water soluble resin) is 0.25 or bigger.
(2) when the ink composite that is at first sprayed in the middle of two kinds of ink composites is cyan ink composition; The content of the green pigment in this cyan ink composition is 2.0 quality % to 4.0 quality % with respect to the total amount of said cyan ink composition, and the mass ratio of crosslinked water soluble resin and green pigment (quality of the quality/green pigment of crosslinked water soluble resin) is 0.40 or bigger.
(3) when the ink composite that is at first sprayed in the middle of two kinds of ink composites is the Yellow ink compsn; The content of the yellow ultramarine in this Yellow ink compsn is 3.0 quality % to 6.0 quality % with respect to the total amount of said Yellow ink compsn, and the mass ratio of crosslinked water soluble resin and yellow ultramarine (quality of the quality/yellow ultramarine of crosslinked water soluble resin) is 0.40 or bigger.
The inventor studies; The result finds when using conventional printing ink group; In some cases; The erasibility of imaging or image possibly reduce, and when being selected from any two kinds of colors in the group of being made up of Yellow ink compsn, magenta ink compositions and cyan ink composition through stack and forming redness, green or blue image, and the colorrendering quality of red, blueness or green image also possibly reduce.When adopting the speed higher than ordinary method to carry out image recording, these trend are especially obvious.According to thinking that its reason maybe be as follows.Promptly; The treatment solution that will contain the composition agglutinative agglutinant that makes in the ink composite, the ink composite that is at first sprayed and the ink composite that then sprayed be applied under the situation on the recording medium successively and first ink composite that at first sprayed by the inadequate situation of treatment solution institute inductive aggegation under; The ink composite that is then sprayed mixes with the ink composite that is at first sprayed, and this will cause the look formation of second kind of color to suffer damage.
According to printing ink group of the present invention; When being selected from any two kinds of colors in the group of forming by Yellow ink compsn, magenta ink compositions and cyan ink composition through stack and forming redness, green or blue image (secondary color image); Can improve the colorrendering quality of redness, blueness or green image, and can not damage the erasibility of imaging and image.When adopting the speed higher than ordinary method to carry out image recording, these effects are especially remarkable.
According to thinking, because the following former thereby colorrendering quality that can obtain to improve.Promptly; The amount of pigment in regulating the ink composite (may also be referred to as first ink composite) at first sprayed and crosslinked water soluble resin is when satisfying above-mentioned requirements (1), (2) or (3); Can improve the compendency (that is, improving agglutination rate) of first ink composite.
According to thinking, owing to can improve the stability of ink composite with the resin-coated pigment of crosslinked water soluble resin lining through mixing pigment wherein, so can obtain imaging effect.
According to thinking,, therefore can obtain the effect of image erasibility owing to can make the ink composite that contains polymerizable compound be solidified to form image through the irradiation of active-energy radiating.Thus, can also improve the tack of image.
The specific embodiments of printing ink group of the present invention can comprise following three embodiments.
First embodiment of printing ink group of the present invention is a kind of like this printing ink group, and it comprises the magenta ink compositions that is at first sprayed as first ink composite, the Yellow ink compsn that is then sprayed or another person and the treatment solution in one (may also be referred to as second ink composite), Yellow ink compsn or the cyan ink composition in the cyan ink composition.In the first embodiment, the magenta ink compositions that is at first sprayed as first ink composite satisfies the requirement (1) of preceding text.
Through the requirement (1) of satisfying preceding text; When magenta ink compositions is sprayed as first ink composite; And thereby Yellow ink compsn or cyan ink composition be ejected at as second tone when forming redness or blue image on the magenta ink compositions that has sprayed, can improve colorrendering quality.
Printing ink group according to first embodiment can only comprise a kind of cyan ink composition, maybe can comprise two kinds or more kinds of cyan ink composition.
Printing ink group according to first embodiment can only comprise a kind of Yellow ink compsn, maybe can comprise two kinds or more kinds of Yellow ink compsn.
Except magenta ink compositions, can also comprise other magenta ink compositions according to the printing ink group of first embodiment as first ink composite.
Second embodiment of printing ink group of the present invention is a kind of like this printing ink group, it comprise as first ink composite and the cyan ink composition that sprayed, as second ink composite and another person and treatment solution in one in magenta ink compositions that is sprayed or the Yellow ink compsn, magenta ink compositions or the Yellow ink compsn.In second embodiment, satisfy the requirement (2) of preceding text as first ink composite and by the cyan ink composition that sprayed.
Through the requirement (2) of satisfying preceding text; When cyan ink composition is sprayed as first ink composite; And thereby magenta ink compositions or Yellow ink compsn be ejected at as second tone when forming blueness or green image on the cyan ink composition that has sprayed, can improve colorrendering quality.
Printing ink group according to second embodiment can only comprise a kind of magenta ink compositions, maybe can comprise two kinds or more kinds of magenta ink compositions.
Printing ink group according to second embodiment can only comprise a kind of Yellow ink compsn, maybe can comprise two kinds or more kinds of Yellow ink compsn.
Except cyan ink composition, can also comprise other cyan ink composition according to the printing ink group of second embodiment as first ink composite.
The 3rd embodiment of printing ink group of the present invention is a kind of like this printing ink group, it comprise as first ink composite and the Yellow ink compsn that sprayed, as second ink composite and another person and treatment solution in one in cyan ink composition that is sprayed or the magenta ink compositions, cyan ink composition or the magenta ink compositions.In the 3rd embodiment, satisfy the requirement (3) of preceding text as first ink composite and by the Yellow ink compsn that sprayed.
Through the requirement (3) of satisfying preceding text; When the Yellow ink compsn is sprayed as first ink composite; And thereby magenta ink compositions or cyan ink composition be ejected at as second tone when forming redness or green image on the Yellow ink compsn that has sprayed, can improve colorrendering quality.
Printing ink group according to the 3rd embodiment can only comprise a kind of cyan ink composition, maybe can comprise two kinds or more kinds of cyan ink composition.
Printing ink group according to the 3rd embodiment can only comprise a kind of magenta ink compositions, maybe can comprise two kinds or more kinds of magenta ink compositions.
Except Yellow ink compsn, can also comprise other Yellow ink compsn according to the printing ink group of the 3rd embodiment as first ink composite.
Except Yellow ink compsn, magenta ink compositions, cyan ink composition and treatment solution; Printing ink group according to first to the 3rd embodiment can also comprise one or more other ink composites, as is selected from the group of being made up of black ink composition, light cyan ink composite, shallow magenta ink compositions and light yellow oil ink composition at least one.As said other ink composite, can use known ink composite and not special restriction.
Particularly; Comprise under the situation of other ink composite in printing ink group, comprise at least that preferably black ink composition is as the printing ink group of said other ink composite (the printing ink group that comprises the ink composite of four kinds or more colors) according to first to the 3rd embodiment.
Below, about printing ink group of the present invention, Yellow ink compsn, magenta ink compositions, cyan ink composition and treatment solution are described.
Be that the center is described with the Yellow ink compsn below, and, can suitably omit the description total with the Yellow ink compsn about the details of magenta ink compositions and cyan ink composition.Except the kind of pigment, each component of magenta ink compositions and cyan ink composition or preferable range each component or the preferable range with the Yellow ink compsn basically are identical.
< Yellow ink compsn >
Printing ink group of the present invention comprises at least a Yellow ink compsn, and said composition contains resin-coated yellow ultramarine, water-soluble polymerizable compound and the water of the water soluble resin lining that yellow ultramarine wherein is crosslinked.
Describe in the face of the various components that contained in this Yellow ink compsn down.
In the following description, the Yellow ink compsn can abbreviate " ink composite " as.
The resin-coated yellow ultramarine of the water soluble resin lining that is crosslinked of yellow ultramarine wherein
The Yellow ink compsn contains the resin-coated yellow ultramarine (hereinafter is also referred to as " specific resin lining yellow ultramarine ") that obtains through following method, and wherein said method comprises to be used water soluble resin dispersion yellow ultramarine and use linking agent to make this water soluble resin crosslinked subsequently.
Specific resin lining yellow ultramarine has the structure of the water soluble resin lining that yellow ultramarine wherein is crosslinked, that is, and and the structure that is crosslinked by water soluble resin lining and said water soluble resin of yellow ultramarine wherein.Here, yellow ultramarine can be by completely or partially lining.Facing the instance of the method for preparing specific resin lining yellow ultramarine down describes.
-yellow ultramarine-
The instance of yellow ultramarine comprises C.I. pigment orange 31, C.I. pigment orange 43, C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. Pigment Yellow 73 15, C.I. pigment yellow 17, C.I. Pigment Yellow 73 74, C.I. Pigment Yellow 73 93, C.I. Pigment Yellow 73 94, C.I. pigment Yellow 12 8, C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 151, C.I. Pigment Yellow 73 155, C.I. Pigment Yellow 73 180 and C.I. Pigment Yellow 73 185.
In the middle of these yellow ultramarines, be preferably selected from C.I. Pigment Yellow 73 74, C.I. Pigment Yellow 73 155 or the C.I. Pigment Yellow 73 185 at least one, and C.I. Pigment Yellow 73 74 most preferably.
In addition, be that the content of yellow ultramarine is 3.0 quality % to 6.0 quality % with respect to the total amount of Yellow ink compsn under the situation as the Yellow ink compsn of first ink composite as stated at the Yellow ink compsn.By this way, can improve the colorrendering quality of secondary color image.
At the Yellow ink compsn is to be used under the situation of the Yellow ink compsn except that first ink composite; As far as not doing special restriction with respect to the content of Yellow ink total composition yellow ultramarine; But consider from the angle of ink stability and illustrative, more preferably in the scope of 3.0 quality % to 6.0 quality %.
In the scope of not damaging effect of the present invention, the Yellow ink compsn can comprise the known pigment except that said yellow ultramarine.
-water soluble resin-
Water soluble resin as the yellow ultramarine that is used to be covered preferably makes yellow ultramarine be dispersed in the water soluble resin dispersion agent in the aqueous medium.
As used among this paper, term " water-soluble " be meant the meltage of 25 ℃ of following resins in zero(ppm) water be 2 quality % or bigger, be preferably 5 quality % or 10 quality % or bigger more greatly and more preferably.Have at resin under the situation of salt forming group, mol alkali or sour neutral dissolving resin degree such as preferably used to be in the scope mentioned above.
The instance of water soluble resin comprises that hydrophilic macromolecule quantizes compound.
The instance of water soluble resin of the present invention comprises polyethylene kind, polyurethanes and polyester.In the middle of these water soluble resins, the preferably polyethylene class.
In addition, preferably have can be through the water soluble resin of the crosslinked functional group of linking agent for water soluble resin of the present invention.
Crosslinkable functional group is not done special restriction, and the example comprises carboxyl or its salt, isocyanide acyl group and epoxy group(ing).Consider preferred carboxyl or its salt, and preferred especially carboxyl from improving dispersed angle.
Water soluble resin with carboxyl preferably uses and contains the multipolymer that carboxylic monomer obtains as the copolymerization component.
The instance that contains carboxylic monomer comprises (methyl) vinylformic acid, propenoic acid beta-carboxyl ethyl ester, fumaric acid, methylene-succinic acid, toxilic acid and Ba Dousuan.In the middle of these monomers, consider preferred (methyl) vinylformic acid or propenoic acid beta-carboxyl ethyl ester from the angle of crosslinkable property and dispersion stabilization.Term " (methyl) vinylformic acid " means at least one in vinylformic acid and the methylacrylic acid.
The copolymerization component that is used to form the water soluble resin with carboxyl preferably includes at least a hydrophobic monomer.The instance of hydrophobic monomer comprises (methyl) alkyl acrylate with 1 to 20 carbon atom, (methyl) propenoate (like (methyl) vinylformic acid benzyl ester or (methyl) vinylformic acid phenoxy ethyl) and vinylbenzene and the verivate thereof with aromatic ring yl.Term " (methyl) propenoate " means at least one in propenoate and the methacrylic ester.Similarly, term " (methyl) alkyl acrylate " means at least one in alkyl acrylate and the alkyl methacrylate; Term " (methyl) vinylformic acid benzyl ester " means at least one in vinylformic acid benzyl ester and the methylacrylic acid benzyl ester; And (methyl) vinylformic acid phenoxy ethyl means in vinylformic acid phenoxy ethyl and the methylacrylic acid phenoxy ethyl at least one.
Though the compound method to multipolymer is not done special restriction, consider the monomeric random polymerization method of preferred vinyl from the angle of dispersion stabilization.
Wherein, Water soluble resin of the present invention preferably uses carboxylic monomer and has (methyl) alkyl acrylate of 1 to 20 carbon atom or have at least one and the multipolymer that obtains in (methyl) propenoate of aromatic ring yl; And be more preferably the multipolymer (that is, containing at least) that the copolymerization through (methyl) vinylformic acid and (methyl) vinylformic acid benzyl ester obtains derived from the formation unit of (methyl) vinylformic acid benzyl ester with derived from the unitary multipolymer of (methyl) acrylic acid formation.
Consider that from the angle of pigment-dispersing water soluble resin is preferably 67mgKOH/g to 200mgKOH/g at the acid number before crosslinked, and 67mgKOH/g to 150mgKOH/g more preferably.
Consider that from the angle of stability and printing ink compendency water soluble resin acid number of (crosslinked water soluble resin) after crosslinked is preferably 55mgKOH/g to 100mgKOH/g.
Water soluble resin is not done special restriction in the weight-average molecular weight before crosslinked, but consider that from the angle of pigment-dispersing its weight-average molecular weight is preferably 3,000 to 100; 000, more preferably 5,000 to 80,000; And even more preferably 10,000 to 60,000.
For example, can use water soluble resin that yellow ultramarine is disperseed yellow ultramarine that is covered with the preparation water soluble resin and the crosslinked specific resin lining yellow ultramarine for preparing of water soluble resin that makes the yellow ultramarine of this water soluble resin lining subsequently by linking agent.
Particularly; For example; Can prepare the pigment dispersion of specific resin lining yellow ultramarine through following preparation method, wherein said preparation method comprises: the aqueous solution that contains alkaline matter is added in the mixture of yellow ultramarine, water soluble resin dispersion agent and organic solvent (it can dissolve or disperse said water soluble resin dispersion agent), the process of dispersion treatment (mixing and hydration step) subsequently; Add to linking agent in the dispersion-s that obtains by dispersion treatment, heat subsequently and crosslinking reaction to obtain the process (cross-linking step) of specific resin lining yellow ultramarine; And with the process (purification step) of the lining yellow ultramarine purifying of the water dispersible specific resin after crosslinked to remove impurity.Through these processes, can be with the yellow ultramarine fine dispersion, thereby can make pigment dispersion with excellent package stability.
More specifically, pigment dispersion can prepare through (for example) disclosed pigment dispersion preparation method in Japanese documentation JP-ANo.2009-190379.
In addition; As stated; At the Yellow ink compsn is to be used under the situation of Yellow ink compsn of first ink composite, and the crosslinked water soluble resin and the mass ratio of yellow ultramarine [quality of the quality/yellow ultramarine of crosslinked water soluble resin] are 0.40 or bigger.By this way, can improve the colorrendering quality of secondary color image.
In addition, consider this mass ratio [quality of the quality/yellow ultramarine of crosslinked water soluble resin] preferably from 0.40 to 0.80 from the angle of imaging.
In addition; At the Yellow ink compsn is to be used under the situation of Yellow ink compsn of first ink composite; Consider from the angle of ink stability; The summation of the content of the content of yellow ultramarine and crosslinked water soluble resin is preferably 4.2 quality % or bigger with respect to the total amount of Yellow ink compsn, and 4.2 quality % to 8.5 quality % more preferably.
In addition; At the Yellow ink compsn is to be used under the situation of the Yellow ink compsn except that first ink composite; Summation to the content of the content of yellow ultramarine and crosslinked water soluble resin is not done special restriction with respect to the Yellow ink total composition; But consider from the angle of image resolution ratio etc., be preferably 3.5 quality % or bigger, and 5.5 quality % to 8.5 quality % more preferably.
In addition; At the Yellow ink compsn is to be used under the situation of the Yellow ink compsn except that first ink composite; Crosslinked water soluble resin and the mass ratio of yellow ultramarine [quality of the quality/yellow ultramarine of crosslinked water soluble resin] are not done special restriction; But consider from the angle of ink stability etc., be preferably 0.40 or bigger, and more preferably 0.40 to 0.80.
Aforementioned water soluble resin can use with non-water-soluble resin (for example, water-insoluble dispersion agent) combination.
Said non-water-soluble resin can be to have hydrophobic formation unit and the unitary water-insoluble resin of hydrophilic formation.Hydrophilic formation unit preferably has the formation unit of acidic-group, and is more preferably the formation unit with carboxyl.
The instance of non-water-soluble resin comprises vinylbenzene and (methyl) acrylic acid multipolymer; The multipolymer of vinylbenzene, (methyl) vinylformic acid and (methyl) propenoate; (methyl) propenoate and (methyl) acrylic acid multipolymer; Polyoxyethylene glycol (methyl) propenoate and (methyl) acrylic acid multipolymer; The multipolymer of vinyl acetate and toxilic acid; And the multipolymer of vinylbenzene and toxilic acid.
More specifically, for example, can preferably use disclosed non-water-soluble resin in Japanese documentation JP-A No.2005-41994,2006-273891,2009-084494 and 2009-191134 in the present invention.
-linking agent-
Specific resin of the present invention lining yellow ultramarine can make resin-coated yellow ultramarine (particularly, the water soluble resin of lining yellow ultramarine in the resin-coated yellow ultramarine) crosslinked and obtain through using linking agent.
Linking agent is not done special restriction, if it be have can with the compound in two or more sites of water soluble resin reaction.From considering that with excellent reactive angle of carboxyl linking agent preferably has the compound (difunctionality or more polyfunctional epoxy compounds) of two or more epoxy group(ing).
The specific examples of linking agent comprises ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, 1,6-hexanediol diglycidyl ether, Diethylene Glycol diglycidylether, polyethyleneglycol diglycidylether, dipropylene glycol diglycidylether, polypropylene glycol diglycidyl ether and trihydroxymethylpropanyltri diglycidyl ether.Linking agent is preferably polyethyleneglycol diglycidylether, Diethylene Glycol diglycidylether or trihydroxymethylpropanyltri diglycidyl ether.
Linking agent can be the commercially available prod.The instance of commercially available prod comprises DENACOLEX-321, EX-821, EX-830, EX-850 and EX-851 (trade(brand)name is by the NagaseChemtex manufactured).
From cross-linked speed and crosslinked after the angle of dispersion stabilization consider; The crosslink part of linking agent (for example; Epoxy group(ing)) and the mol ratio of treating crosslink part (for example, carboxyl) of water soluble resin is preferably 1: 1.1 to 1: 10, more preferably 1: 1.1 to 1: 5 and further be preferably 1: 1.1 to 1: 3.
The median size of specific resin of the present invention lining yellow ultramarine is preferably 10nm to 200nm, more preferably 10nm to 150nm, also more preferably 40nm to 150nm even more preferably 50nm to 150nm and being preferably especially in the scope of 50nm to 130nm.When median size is 200nm or more hour, can improve colorrendering quality, and can improve the ejection when spraying through ink jet method.When median size is 10nm or when bigger, can improve photostabilization (1ight-fastness).In addition, the size-grade distribution of specific resin lining yellow ultramarine is not done concrete restriction, can use any one that has in wide size-grade distribution or the distribution of single fineness of dispersion.In addition, can mix two kinds of uses or more kinds of specific resin lining yellow ultramarine with single fineness of dispersion distribution.
Here, the median size of specific resin lining yellow ultramarine is represented the median size of the specific resin lining yellow ultramarine of printing ink state, and above-mentioned preferable range also goes for the so-called concentrated ink dispersion as previous stage in printing ink stage.
Use NANOTRAC particle size distribution analysis appearance UPA-EX150 (making),, thereby calculate the median size and the size-grade distribution of specific resin lining yellow ultramarine of the present invention according to the equal particle diameter of dynamic light scattering method measuring body by Nikkiso Co., Ltd..
Water-soluble polymerizable compound
Yellow ink compsn of the present invention contains at least a water-soluble polymerizable compound.
As used among this paper, term " water-soluble " is meant that said compound is dissolved in the water with the amount that produces certain concentration.Particularly, the solubleness of this compound in 25 ℃ water is preferably 5 quality % or bigger and 10 quality % or bigger more preferably.The compound of preferably dissolving in aqueous ink compsn of water-soluble polymerizable compound in addition, (preferably dissolving equably).Water-soluble polymerizable compound can be such compound, and its solubleness increases because of the water-miscible organic solvent that adds the hereinafter description, thereby dissolving (preferably dissolving equably) is in ink composite.
As water-soluble polymerizable compound of the present invention; Said composition preferably includes and is selected from least a in the group that the compound that has (methyl) acrylic amide structure in the compound that has (methyl) acrylate structural by in its molecule and its molecule forms, and more preferably comprises the compound that has (methyl) acrylic amide structure at least a its molecule.As used among this paper; Term " (methyl) acrylate structural " is meant at least one in metacrylic acid ester structure and the acrylate structural, and term " (methyl) acrylic amide structure " is meant in methacryloyl amine structure and the acrylic amide structure at least one.
Have in-its molecule the compound of (methyl) acrylate structural-
Polymerizable compound to having (methyl) acrylate structural in its molecule is not done special restriction, as long as it is the water-soluble polymerizable compound that has (methyl) acrylate structural in its molecule.
The polymerizable compound that has (methyl) acrylate structural in its molecule is preferably by the compound shown in the following formula (M-1).
In formula (M-1), Q
1Represent the i valency to connect base, R
1Represent Wasserstoffatoms or methyl, and i represents 1 or bigger integer.
By the compound shown in the formula (M-1) be wherein unsaturated monomer by ester bond be connected basic Q
1The compound that connects.R
1Represent Wasserstoffatoms or methyl, and preferably represent Wasserstoffatoms.To connecting basic Q
1Valence state i do not do special restriction, but preferably 2 or bigger, more preferably 2 to 6, and even more preferably 2 to 4.
To connecting basic Q
1Do not do special restriction, as long as it can be connected with (methyl) acrylate structural, but Q
1Be preferably selected from the connection base that makes compound shown in the formula (M-1) satisfy water solubility as discussed above.Q
1Specific examples comprise from the compound that is selected from following compound group X the residue of eliminating one or more Wasserstoffatomss or hydroxyl and obtaining.
-compound group X-
Compound group X comprises: polyvalent alcohol, like terepthaloyl moietie, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, Ucar 35, dipropylene glycol, tripropylene glycol, W 166,1, ammediol, 1,2-butyleneglycol, 1; 3-butyleneglycol, 1,4-butyleneglycol, 2,3-butyleneglycol, 1,5-pentanediol, 1; 4-pentanediol, 2,4-pentanediol, 3-methyl isophthalic acid, 5-pentanediol, 2-methyl-2,4-pentanediol, 1; 5-pinakon, 1,6-pinakon, 2,5-pinakon, USP Kosher, 1; 2,4-trihydroxybutane, 1,2; 6-hexanetriol, 1,2,5-penta triol, mercaptoethanol, TriMethylolPropane(TMP), ditrimethylolpropane, trimethylolethane, two trimethylolethane, NSC 6366, tetramethylolmethane, NSC 65881, its condenses, low molecular weight polyethylene alcohol and sugar; And polyamines, like quadrol, NSC 446, Triethylenetetramine (TETA), polyethylene imine based and gather tn.
Connect basic Q
1Instance also comprise having 4 or the still less replacement or the unsubstituted alkylidene chain of carbon atom, like methylene radical, ethylidene, propylidene or butylidene; And has a functional group saturated or unsaturated heterocycle (like pyridine ring, imidazole ring, pyrazine ring, piperidine ring, piperazine ring or morpholine ring).
Wherein, connect basic Q
1Preferably contain the residue of polyol of oxyalkylene group (preferred oxygen vinyl), and especially preferably contain the residue of polyol of three or more a plurality of oxyalkylene group (preferred oxygen vinyl).
The specific examples that has the water-soluble polymerizable compound of (methyl) acrylate structural in its molecule includes but not limited to following non-ionic compound.
The instance of nonionic polymerizable compound also comprises (methyl) esters of acrylic acid that a part, has at least two acryls from the polyol compound deutero-.The instance of said polyol compound comprises the polyol compound with at least two hydroxyls, like the condenses of glycol, oligomeric ethers and oligomer ester class, monose and disaccharides.
In addition, (methyl) propenoate of also preferred trolamine, diethylolamine, three hydroxylamino methane or three hydroxylamino ethane.
Have in-its molecule the compound of (methyl) acrylic amide structure-
Compound to having (methyl) acrylic amide structure in its molecule is not done special restriction, as long as it is the polymerizable compound that has (methyl) acrylic amide structure in its molecule.
Has the compound shown in the formula (M-2) that the compound of (methyl) acrylic amide structure preferably provides by hereinafter in its molecule.Structure with formula (M-2) can be so that being increased by compound shown in the formula (1) and the consistency between the polymerizable compound of describing of hereinafter, thereby can preferably strengthen and solidify susceptibility etc.
In formula (M-2), Q
2Represent the j valency to connect base, R
2Represent Wasserstoffatoms or methyl, and j represents 1 or bigger integer.
By the compound shown in the formula (M-2) be wherein unsaturated monomer by amido linkage be connected basic Q
2The compound that connects.R
2Represent Wasserstoffatoms or methyl, and preferably represent Wasserstoffatoms.To connecting basic Q
2Valence state j do not do special restriction, but preferably 2 or bigger, more preferably 2 to 6, and even more preferably 2 to 4.
To connecting basic Q
2Do not do special restriction, as long as it can be connected with (methyl) acrylic amide structure.Connect basic Q
2Details be connected basic Q
1Details identical, and embodiment preferred is also identical.
The specific examples that has the water-soluble polymerizable compound of (methyl) acrylic amide structure in its molecule comprises following water-soluble polymerizable compound.
Ink composite can comprise compound, the compound with sulfonamide structure with maleimide amine structure, the compound with N-vinyl acetamide structure etc.
Water-soluble polymerizable compound of the present invention is preferably difunctionality or more polyfunctional compound as stated.Consider that from the angle that improves erasibility water-soluble polymerizable compound is preferably the functional monomer of difunctionality to six, and from realizing that the two angle of solubleness and erasibility considers, preferably the functional monomer of difunctionality to four.
Can use a kind of water-soluble polymerizable compound maybe can make up separately and use two kinds or more kinds of water-soluble polymerizable compound.
The content of water-soluble polymerizable compound in ink composite is preferably 4 quality % to 30 quality %, and 15 quality % to 25 quality % more preferably.
About the content ratio of water-soluble polymerizable compound with respect to the solid substance of pigment, the ratio of the solid substance of pigment and the content of water-soluble polymerizable compound is preferably 1: 1 to 1: 30, and more preferably 1: 3 to 1: 15.If the content of polymerizable compound is equal to or greater than the content of pigment, then image intensity can further improve, thereby causes excellent image erasibility.If the content of polymerizable compound is below 30 times of pigment content, be favourable aspect the pile height (pileheight) then.
In water-soluble polymerizable compound of the present invention; Consider from the angle of solidifying the sensitivity and the anti-adhesive of the image that will form; The molecular weight of polymerizable compound is with respect to the ratio of the number of polymerizable functional group contained in the compound individual molecule; That is the value that obtains divided by the number of polymerizable functional group contained in a part of the molecular weight of the water-soluble polymerizable compound (number of the polymerizable functional group of the molecular weight of polymerizable compound/contained; Sometimes be also referred to as " A value "), preferably 175 or littler, and be more preferably 165 or littler.See A value preferably 84 or bigger from the viewpoint of structure.
For example; For some specific examples of aforementioned water-soluble polymerizable compound, the A value as follows: 172.2), polymerizable compound 2 (A value: 164.2), polymerizable compound 3 (A value: 84.1), polymerizable compound 34 (A value: 154.1), polymerizable compound 35 (A value: 164.2) and polymerizable compound 36 (A value: 142.2) polymerizable compound 1 (A value:.
Consider that from the angle of solidifying sensitivity and resistance to blocking the preferably such compound of water-soluble polymerizable compound of the present invention: it has two or more polymerizable functional group and A values that are selected from the group of being made up of (methyl) acrylamido, dimaleoyl imino, ethene sulfuryl and N-vinylamide base is 175 or littler; Be more preferably such compound, it has two or more polymerizable functional group and A values that are selected from the group of being made up of (methyl) acrylamido, dimaleoyl imino, ethene sulfuryl and N-vinylamide base is 84 to 175; Even being more preferably such compound, it has two or more polymerizable functional group and A values that are selected from the group of being made up of (methyl) acrylamido, dimaleoyl imino, ethene sulfuryl and N-vinylamide base and is more than or equal to 84 and is less than or equal to 165; And especially preferably have two or more (methyl) acrylamidos at least and A value and be 84 to 165 compound.
The compound that water-soluble polymerizable compound is preferably such, it has two or more polymerizable functional group and non-ionic hydrophilic group and A values that are selected from the group of being made up of (methyl) acrylamido, dimaleoyl imino, ethene sulfuryl and N-vinylamide base is 84 to 175; Be more preferably such compound, it has two or more polymerizable functional group and at least a non-ionic hydrophilic group and A values that are selected from oxyalkylene group, its oligopolymer and hydroxyl that are selected from the group of being made up of (methyl) acrylamido, dimaleoyl imino, ethene sulfuryl and N-vinylamide base is 84 to 165; And special preferably such compound, it has two or more (methyl) acrylamidos and at least a non-ionic hydrophilic group and the A value that is selected from the group of being made up of oxyalkylene group, its oligopolymer and hydroxyl is 84 to 165.
Photoepolymerizationinitiater initiater
Yellow ink compsn of the present invention preferably contains at least a Photoepolymerizationinitiater initiater.
Photoepolymerizationinitiater initiater is water-soluble photo-polymerization initiator preferably.
As used among this paper, for Photoepolymerizationinitiater initiater, term " water-soluble " is meant that this Photoepolymerizationinitiater initiater meltage in zero(ppm) water under 25 ℃ is 0.5 quality % or bigger.Water-soluble photo-polymerization initiator meltage in zero(ppm) water under 25 ℃ is preferably 1 quality % or bigger, and 3 quality % or bigger more preferably.
In addition, as Photoepolymerizationinitiater initiater, can use suitably and can pass through the water-soluble polymerizable compound polymeric Photoepolymerizationinitiater initiater of active-energy radiation (for example, ultraviolet ray) initiation.
The instance of water-soluble photo-polymerization initiator comprise by the compound shown in the following formula (1) and in Japanese documentation JP-A No.2005-307198 disclosed compound.In the middle of these compounds, consider from the angle of adhesivity and erasibility, preferably by the water-soluble photo-polymerization initiator shown in the following formula (1).
In formula (1), m and n represent 0 or bigger integer independently of one another, and m+n represents 0 to 3 integer.Preferably, m represents 0 to 3, and n represents 0 or 1.More preferably, m represents 0 or 1, and n represents 0.
Hereinafter provides the specific examples of compound shown in the formula (1), but the invention is not restricted to this.
Compound shown in the formula (1) can be that (for example) is according to middle disclosed method synthetic compounds such as Japanese documentation JP-A No.2005-307198.Compound shown in the formula (1) can be the commercial compound.Examples for compounds shown in the commercially available formula (1) can be IRGACURE2959 (m=0, n=0).
The content of Photoepolymerizationinitiater initiater in Yellow ink compsn of the present invention is preferably 0.1 quality % to 30 quality %, more preferably 0.5 quality % to 20 quality % even 1.0 quality % to 15 quality % and most preferably be 1.0 quality % to 5.0 quality % more preferably in solid substance.
Tensio-active agent
Yellow ink compsn of the present invention preferably contains at least a tensio-active agent.This tensio-active agent can be used as surface tension modifier.
As surface tension modifier, can use its intramolecularly to possess the compound of the structure that contains hydrophilic segment and hydrophobic part effectively.Can use any one in AS, cats product, amphoterics, nonionogenic tenside or the beet alkali surface activator.
Among the present invention, consider preferred nonionic surfactants from the view of disturbances between the ink composite drop that suppresses to eject.In the middle of nonionogenic tenside, more preferably acetylenediol tensio-active agent.
The instance of acetylenediol tensio-active agent comprises 2,4,7,9-tetramethyl--5-decine-4, and 7-two is pure and mild 2,4,7,9-tetramethyl--5-decine-4, the oxyalkylene addition compound of 7-glycol.Be preferably selected from wherein at least one as the acetylenediol tensio-active agent.The instance of the commercially available prod of these compounds comprises the E series of being made by Nissin Chemical Industry Co., Ltd., like OLFINEE1010 (trade(brand)name; Make by Nissin Chemical Industry Co., Ltd.).
When mixing tensio-active agent (surface tension modifier) in the Yellow ink compsn; Consider that from the angle of advantageously spraying the Yellow ink compsn through ink ejecting method the surface tension that the incorporation of tensio-active agent can be regulated ink composite makes it preferably to drop in the scope of 20mN/m to 60mN/m.Surface tension is more preferably in the scope of 20mN/m to 45mN/m, and 25mN/m to 40mN/m more preferably.
Content to tensio-active agent in the Yellow ink compsn is not done special restriction, and this content preferably is in the capillary scope that can obtain aforementioned range.The content of tensio-active agent is preferably 0.1 quality % or bigger in the said ink composite, 0.1 quality % to 10 quality % more preferably, and 0.2 quality % to 3 quality % more preferably.
Water-miscible organic solvent
Yellow ink compsn of the present invention contains water, and outside dewatering, can randomly contain at least a water-miscible organic solvent.
Use water-miscible organic solvent to provide and prevent drying and promote effect wetting or infiltration.In order to prevent drying, water-miscible organic solvent can be as anti-siccative, and it can prevent because of printing ink adheres in the jet orifice of nozzle, eyelet is stopped up in drying and aggegation.For prevent drying and promote wetting, the preferred low water-miscible organic solvent of steaming pressure ratio water.In order to promote infiltration, water-miscible organic solvent can be as strengthening the penetration enhancer of printing ink to the penetrating power of paper.
The instance of water-miscible organic solvent comprises: alkanediol (polyvalent alcohol), like USP Kosher, terepthaloyl moietie and Ucar 35; Sugar alcohol; Alkyl alcohol with 1 to 4 carbon atom is like ethanol, methyl alcohol, butanols, propyl alcohol and Virahol; And glycol ethers, like methyl glycol, glycol monoethyl ether, ethylene glycol monobutyl ether, methyl glycol acetate, methyl carbitol, Diethylene Glycol one ether, Diethylene Glycol one positive propyl ether, terepthaloyl moietie one isopropyl ether, Diethylene Glycol one isopropyl ether, terepthaloyl moietie one n-butyl ether, terepthaloyl moietie one uncle's butyl ether, Diethylene Glycol one uncle's butyl ether, triethylene glycol one ether, 1-methyl isophthalic acid-methoxybutanol, Ucar 35 monomethyl ether, propylene glycol monoethyl ether, Ucar 35 one uncle's butyl ether, Ucar 35 one positive propyl ether, Ucar 35 one isopropyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol one ether, dipropylene glycol one positive propyl ether, dipropylene glycol one isopropyl ether and tripropylene glycol monomethyl ether.Can use a kind of in these water-miscible organic solvents separately, maybe can make up wherein two or more of use.
Other component
Except that the component that preceding text are mentioned, Yellow ink compsn of the present invention can further randomly contain one or more other components.The instance of other component comprises colloid silica, resin particle and various additive.
When Yellow ink compsn of the present invention contains colloid silica, can improve jetting stability, and can prevent the deterioration of fluid-repellency in the ink gun parts.Particularly, at least a portion of ink gun parts, used under the organosilyl situation, mixed the special significant effective of colloid silica.
As colloid silica, for example, can use disclosed known colloid silica among the Japanese documentation JP-A No.2002-206063.
Resin particle preferably has following function: when being applied with treatment solution and exsiccant recording medium zone on treatment solution that resin particle and hereinafter are mentioned or its when contacting; The own aggegation of resin particle or make its dispersion state unstable; Thereby increased ink viscosity; Thereby make said ink composite (that is image) photographic fixing.This type of resin particle preferably is scattered in in water or the organic solvent at least one.
The instance of resin particle comprises acrylic resin particle; The vinyl acetate resin particle; The styrene butadiene resin particle; Vinyl chloride resin granules; Vinylformic acid-styron particle; The butadiene resin particle; The styron particle; Crosslinked acrylic resin particle; Crosslinked styron particle; The benzo guanamine resin particle; Phenolic resin particle; The silicone resin particle; Epoxy particles; Urethane resin particles; The paraffin resin particle; Any one latex in fluorinated resin particle and these resins.Its preferred embodiment comprises acrylic resin particle, vinylformic acid-styron particle, styron particle, crosslinked acrylic resin particle and crosslinked styron particle.
Resin particle can use with the form of latex.
The weight-average molecular weight of resin particle is preferably 10,000 to 200,000, and more preferably 20,000 to 200,000.
The median size of resin particle is preferably 1nm to 1 μ m, more preferably 1nm to 200nm, 1nm to 100nm and be preferably 1nm to 50nm especially more preferably also.
The second-order transition temperature of resin particle (Tg) is preferably 30 ℃ or higher, and more preferably 40 ℃ or higher, and more preferably 50 ℃ or higher.
Consider that from the angle that more effectively realizes effect of the present invention the content of resin particle is preferably 5 quality % or littler, 3 quality % or littler and be preferably 1 quality % or littler especially more preferably with respect to the total amount of ink composite.
The instance of various additives comprises known additives, like UV light absorber, anti-decolourant, mould inhibitor, pH regulator agent, inhibitor, inhibitor, emulsion stabilizer, sanitas, skimmer, viscosity modifier, dispersion stabilizer and sequestrant.These content of additive can suitably be confirmed according to required should being used for.For example, every kind of content of additive can be 0.02 quality % to 1.00 quality % in black ink composition.
The instance of UV light absorber comprises Benzophenones UV light absorber, benzotriazole category UV light absorber, salicylate class UV light absorber, cyanoacrylate UV light absorber and nickel complexing salt UV light absorber.
As anti-decolourant, can use multiple organic anti-decolourant and the anti-decolourant of metal complex.The instance of organic anti-decolourant comprises hydroquinones, alkoxyl group phenols, dialkoxy phenols, phenols, phenyl amines, amine, indane class, chromogen alkanes, alkoxy benzene amine and heterocyclic.The instance of metal complex comprises nickel complex and zinc complex.
The instance of mould inhibitor comprises Sodium dehydroacetate, Sodium Benzoate, pyrithione-1-sodium oxide, ethylparaben, 1,2-benzisothiazole-3-ketone, sodium sorbate and Witophen N.
Special restriction is not done in the pH regulator agent,, and can not brought spinoff to get final product ink composite as long as it can be controlled to required value with pH.The pH regulator agent can suitably select according to purpose.The instance of pH regulator agent comprises: alcamines (for example, diethylolamine, trolamine and 2-amino-2-ethyl-1, ammediol); Alkali metal hydroxide (for example, Lithium Hydroxide MonoHydrate, sodium hydroxide and Pottasium Hydroxide); Ammonium oxyhydroxide (for example, volatile caustic and quaternary ammonium hydroxide); Phosphorus oxyhydroxide; And alkaline carbonate.
The instance of inhibitor comprises acid accumulator sulfite, Sulfothiorine, sulfo-diglycollic acid ammonium, di-isopropyl ammonium nitrite, trinitrol and dicyclohexyl ammonium nitrite.
The instance of inhibitor comprises phenol antioxidant (comprising sterically hindered phenolic antioxidant), amine antioxidants, sulphur class inhibitor and inferior Phosphorus inhibitor.
The instance of sequestrant comprises sodium ethylene diamine tetracetate; Sodium nitrilo triacetate; AEEA tetraacethyl sodium; Diethylene triaminepentaacetic acid(DTPA) sodium; And uramildiacetic acid sodium.
The character of Yellow ink compsn
The surface tension of Yellow ink compsn of the present invention (25 ℃) is preferably 20mN/m to 60mN/m, more preferably 20mN/m to 45mN/m and 25mN/m to 40mN/m more preferably.
Surface tension uses automatic surface tonometer CBVP-Z (trade(brand)name is made by KyowaInterface Science Co., Ltd.) to measure under 25 ℃ the condition.
The viscosity of Yellow ink compsn of the present invention under 25 ℃ is preferably 1.2mPa.s to 15.0mPa.s, more preferably more than or equal to 2mPa.s and less than 13mPa.s, and more preferably more than or equal to 2.5mPa.s and less than 10mPa.s.
The viscosity of Yellow ink compsn uses VISCOMETER TV-22 (trade(brand)name is made by Toki Sangyo Co., Ltd.) to measure ink composite to be measured being adjusted under 25 ℃ the condition.
The preparation method
The Yellow ink compsn can prepare through domestic method.For example, can prepare said ink composite through pigment dispersion, at least a water-soluble polymerizable compound and water and Photoepolymerizationinitiater initiater as required, water-miscible organic solvent and the tensio-active agent that mixing contains specific resin lining yellow ultramarine.Blending means is not done special restriction, can select to use blending means commonly used aptly.
< magenta ink compositions >
Printing ink group of the present invention comprises at least a magenta ink compositions, and said composition contains resin-coated magenta pigment, water-soluble polymerizable compound and the water of the water soluble resin lining that magenta pigment wherein is crosslinked.
The resin-coated magenta pigment of the water soluble resin lining that is crosslinked of magenta pigment wherein
Magenta ink compositions contains the resin-coated magenta pigment (hereinafter is also referred to as " specific resin lining magenta pigment ") that obtains through following method, and wherein said method comprises uses water soluble resin to disperse magenta pigment and use linking agent to make this water soluble resin crosslinked subsequently.
Specific resin lining magenta pigment has the structure of the water soluble resin lining that magenta pigment wherein is crosslinked, that is, wherein magenta pigment by the water soluble resin lining and wherein water soluble resin crosslinked structure takes place.Here, magenta pigment can be by completely or partially lining.The instance of method that is used to prepare said specific resin lining magenta pigment is identical with the method that is used to prepare specific resin lining yellow ultramarine, and difference is to use magenta pigment to replace the specific resin yellow ultramarine among the yellow ultramarine preparation method that is covered.
-magenta pigment-
The instance of magenta pigment comprises C.I. Pigment red 2; C.I. pigment red 3; C.I. Pigment red 5; C.I. Pigment red 6; C.I. Pigment red 7; C.I. Pigment red 15; C.I. Pigment red 16; C.I. pigment red 4 8:1; C.I. Pigment red 53:1; C.I. Pigment red 57:1; C.I. pigment red 122; C.I. pigment red 123; C.I. Pigment red 139; C.I. Pigment red 144; C.I. pigment red 149; C.I. Pigment red 166; C.I. Pigment red 177; C.I. Pigment red 178; C.I. Pigment red 222 and C.I. pigment violet 19.
In the middle of these magenta pigment, consider from the angle of tackiness and erasibility, be preferably selected from C.I. pigment red 122, C.I. Pigment red 202, C.I. Pigment red 209 and the C.I. pigment violet 19 at least one.
At magenta ink compositions is to be used under the situation of magenta ink compositions of first ink composite, and the content of magenta pigment is 4.2 quality % to 6.0 quality % with respect to the total amount of magenta ink compositions.By this way, can improve the colorrendering quality of secondary color.When the content of magenta pigment is 4.2 quality % or when bigger, can also improve the colorrendering quality of magenta monochrome image.
At magenta ink compositions is to be applied under the situation of the magenta ink compositions except that first ink composite; Magenta pigment content to respect to the magenta ink compositions total amount is not done special restriction; But consider that from the angle of image resolution ratio etc. this content is 4.2 quality % to 6.0 quality % more preferably.
In the scope of not damaging effect of the present invention, magenta ink compositions can comprise the known pigment except that said magenta pigment.
-water soluble resin-
Water soluble resin as the magenta pigment that is used to be covered preferably makes magenta pigment be dispersed in the water soluble resin dispersion agent in the aqueous medium.
The preferable range of water soluble resin of magenta pigment of being used to be covered is identical with the preferable range of the water soluble resin of the yellow ultramarine that is used to be covered.
In addition; As stated; At magenta ink compositions is to be used under the situation of magenta ink compositions of first ink composite, and the crosslinked water soluble resin and the mass ratio of magenta pigment [quality of the quality/magenta pigment of crosslinked water soluble resin] are 0.25 or bigger.By this way, can improve the colorrendering quality of secondary color.When this mass ratio is 0.25 or when bigger, also improved the colorrendering quality of magenta monochrome image.
In addition, consider this mass ratio [quality of the quality/magenta pigment of crosslinked water soluble resin] preferably 0.25 to 0.6 from the angle of illustrative.
In addition; At magenta ink compositions is to be used under the situation of magenta ink compositions of first ink composite; Consider from the angle of ink stability; The summation of the content of the content of magenta pigment and crosslinked water soluble resin is preferably 5.25 quality % or bigger with respect to the total amount of magenta ink compositions, and 5.25 quality % to 8.0 quality % more preferably.
In addition; At magenta ink compositions is to be used under the situation of the magenta ink compositions except that first ink composite; What being to the summation of the content of magenta pigment and resin content with respect to the total amount of magenta ink compositions does not do special restriction; But consider preferred 5.5 quality % or bigger, and more preferably 5.5 quality % to 8.0 quality % from the angle of the colorrendering quality of image.
In addition; At magenta ink compositions is to be used under the situation of the magenta ink compositions except that first ink composite; Crosslinked water soluble resin and the mass ratio of magenta pigment [quality of the quality/magenta pigment of crosslinked water soluble resin] are not done special restriction; But consider from the angle of ink stability etc., be preferably greater than 0.25, and more preferably greater than 0.25 and be less than or equal to 0.6.
The median size of specific resin of the present invention lining magenta pigment is preferably 10nm to 200nm, more preferably 10nm to 150nm, also more preferably 50nm to 150nm even more preferably 50nm to 120nm; Further preferred 50nm to 100nm, and preferred especially 50nm to 90nm.If median size is 200nm or littler, then can improves colorrendering quality, and can improve the ejection when spraying through ink ejecting method.If median size is 10nm or bigger, then can improve photostabilization.In addition, the size-grade distribution of specific resin lining magenta pigment is not done special restriction, can use to have in distributing any of wide size-grade distribution or single fineness of dispersion.In addition, can mix two kinds of uses or more kinds of specific resin lining magenta pigment with single fineness of dispersion distribution.
The median size of specific resin lining magenta pigment is represented the median size of the specific resin lining magenta pigment of printing ink state, and above-mentioned preferable range also goes for the so-called magenta pigment dispersion-s as previous stage in printing ink stage.
Use NANOTRAC particle size distribution analysis appearance UPA-EX150 (trade(brand)name; Make by Nikkiso Co., Ltd.), according to the equal particle diameter of dynamic light scattering method measuring body, thereby obtain the median size and the size-grade distribution of specific resin lining magenta pigment of the present invention.
About magenta ink compositions, each component except that aforementioned component (water-soluble polymerizable compound and Photoepolymerizationinitiater initiater, tensio-active agent, water-miscible organic solvent and other component that can choose use wantonly) and the preferable range (comprising the preparation method) of preferable range and magenta ink compositions thereof are identical with aforementioned Yellow ink compsn.
< cyan ink composition >
Printing ink group of the present invention comprises at least a cyan ink composition, and said composition contains resin-coated green pigment, water-soluble polymerizable compound and the water of the water soluble resin lining that green pigment wherein is crosslinked.
The resin-coated green pigment of the water soluble resin lining that is crosslinked of green pigment wherein
Cyan ink composition contains the resin-coated green pigment (hereinafter is also referred to as " specific resin lining green pigment ") that obtains through following method, and wherein said method comprises uses water soluble resin to disperse green pigment and use linking agent to make the dispersive water soluble resin crosslinked subsequently.
Specific resin lining green pigment has the structure of the water soluble resin lining that green pigment wherein is crosslinked, that is, wherein green pigment by the water soluble resin lining and wherein water soluble resin crosslinked structure takes place.Here, green pigment can be by completely or partially lining.The instance of method that is used to prepare specific resin lining green pigment is identical with the method that is used to prepare specific resin lining yellow ultramarine, and difference is to use green pigment to replace the specific resin yellow ultramarine among the yellow ultramarine preparation method that is covered.
-green pigment-
The instance of green pigment comprises C.I. pigment Blue 15, C.I. pigment Blue 15: 2, C.I. pigment Blue 15: 3, C.I. pigment Blue 15: the silicone cross-linked aluminium phthalocyanine of 4, describing in C.I. pigment blue 16, C.I. pigment blue 60, C.I. pigment Green 7 and the United States Patent(USP) No. 4311775.
In the middle of these green pigments, be preferably selected from the C.I. pigment Blue 15: 3, C.I. pigment Blue 15: 4 or C.I. pigment blue 16 at least one, and preferred especially C.I. pigment Blue 15: 3 or the C.I. pigment Blue 15: at least one in 4.
At cyan ink composition is to be used under the situation of cyan ink composition of first ink composite, and the content of green pigment is 2.0 quality % to 4.0 quality % with respect to the total amount of cyan ink composition.By this way, can improve the colorrendering quality of secondary color.
In addition; At cyan ink composition is to be applied under the situation of the cyan ink composition except that first ink composite; Green pigment is not done special restriction with respect to the content of cyan ink composition total amount; But consider from the angle of image resolution ratio etc., more preferably 2.0 quality % to 4.0 quality %.
In the scope of not damaging effect of the present invention, cyan ink composition can comprise the known pigment except that said green pigment.
-water soluble resin-
Water soluble resin as the lining green pigment preferably makes green pigment be dispersed in the water soluble resin dispersion agent in the aqueous medium.
The preferable range of water soluble resin of green pigment of being used to be covered is identical with the preferable range of the water soluble resin of the yellow ultramarine that is used to be covered.
At cyan ink composition is to be used under the situation of cyan ink composition of first ink composite, and the crosslinked water soluble resin and the mass ratio of green pigment [quality of the quality/green pigment of crosslinked water soluble resin] are 0.40 or bigger.By this way, improved the colorrendering quality of secondary color.
Consider this mass ratio [quality of the quality/green pigment of crosslinked water soluble resin] preferably 0.40 to 0.80 from the angle of illustrative.
At cyan ink composition is to be used under the situation of cyan ink composition of first ink composite; Consider from the angle of ink stability; The summation of the content of the content of green pigment and crosslinked water soluble resin is preferably 2.8 quality % or bigger with respect to the total amount of cyan ink composition, and 2.8 quality % to 5.0 quality % more preferably.
At cyan ink composition is to be used under the situation of the cyan ink composition except that first ink composite; What being to the summation of the content of the content of green pigment and crosslinked water soluble resin with respect to the total amount of cyan ink composition does not do special restriction; But consider from the angle of image resolution ratio etc.; Preferred 2.8 quality % or bigger, and more preferably 2.8 quality % to 6.0 quality %.
At cyan ink composition is to be used under the situation of the cyan ink composition except that first ink composite; Crosslinked water soluble resin and the mass ratio of green pigment [quality of the quality/green pigment of crosslinked water soluble resin] are not done special restriction; But consider from the angle of image resolution ratio etc.; Be preferably 0.40 or bigger, and more preferably 0.40 to 0.80.
The median size of specific resin of the present invention lining green pigment is preferably 10nm to 200nm, more preferably 10nm to 150nm, also more preferably 40nm to 150nm, also further preferred 50nm to 150nm even more preferably 50nm to 120nm, further preferred 50nm to 100nm, and preferred especially 50nm to 90nm.If median size is 200nm or littler, then can improves colorrendering quality, and can improve the ejection when spraying through ink ejecting method.If median size is 10nm or bigger, then can improve photostabilization.Size-grade distribution to specific resin lining green pigment is not done special restriction, can use to have in distributing any of wide size-grade distribution or single fineness of dispersion.In addition, can mix two kinds of uses or more kinds of specific resin lining green pigment with single fineness of dispersion distribution.
Here, the median size of specific resin lining green pigment is represented the median size of the specific resin lining green pigment of printing ink state, and above-mentioned preferable range also goes for the so-called concentrated ink dispersion as previous stage in printing ink stage.
Use NANOTRAC particle size distribution analysis appearance UPA-EX150 (trade(brand)name; Make by Nikkiso Co., Ltd.), according to the equal particle diameter of dynamic light scattering method measuring body, thereby obtain the median size and the size-grade distribution of specific resin lining green pigment of the present invention.
About cyan ink composition, each component except that aforementioned component (water-soluble polymerizable compound and Photoepolymerizationinitiater initiater, tensio-active agent, water-miscible organic solvent and other component that can choose use wantonly) and the preferable range (comprising the preparation method) of preferable range and cyan ink composition thereof are identical with aforementioned Yellow ink compsn.
< treatment solution >
Printing ink group of the present invention comprises treatment solution, and this treatment solution contains makes component agglutinative agglutinant contained in the ink composite.
This treatment solution comprises at least a agglutinant that when contacting with aforementioned ink composite, can form agglomeration, and randomly can also comprise one or more other components.
This agglutinant with recording medium on ink composite can make component aggegation (photographic fixing) contained in the ink composite when contacting.Agglutinant can (for example) play a role as fixing salt.For example; When treatment solution being applied on the recording medium (paper preferably is covered); And when further being applied to ink composite on the recording medium that has agglutinant above it, this ink composite contact with agglutinant and ink composite in the component aggegation and be fixed on this recording medium.
The instance of agglutinant comprises acidic cpd, polyvalent metal salt and cationic polymers.In the middle of these agglutinants, consider the preferred acidic compound from the agglutinative angle of ink composite component.Can use a kind of agglutinant separately, maybe can make up and use two kinds or more kinds of agglutinant.
-acidic cpd-
The preferred embodiment of acidic cpd comprises sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, ROHM, acetate, oxyacetic acid, propanedioic acid, oxysuccinic acid, toxilic acid, xitix, succsinic acid, pentanedioic acid, fumaric acid, Hydrocerol A, tartrate, lactic acid, sulfonic acid, ortho-phosphoric acid, metaphosphoric acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrroles's carboxylic acid, furancarboxylic acid, pyridine carboxylic acid, coumalic acid, thiophene carboxylic acid, nicotinic acid and their verivate.
Especially, the high acidic cpd of preferably water dissolubility.From considering preferably have the acidic cpd of 3 valencys or littler valence state with the ink composite component reaction with the angle of whole printing ink photographic fixing.The acidic cpd that especially preferably has divalent or 3 valencys.
Can use a kind of acidic cpd separately, maybe can make up and use two kinds or more kinds of acidic cpd.
When treatment solution contained acidic cpd, the pH of treatment solution (25 ℃) was preferably 0.1 to 6.8, more preferably 0.5 to 6.0 and more preferably 0.8 to 5.0.
The content of acidic cpd is preferably 40 quality % or littler with respect to the total amount of treatment solution, 15 quality % to 40 quality % more preferably, even 15 quality % to 35 quality % more preferably.When the content of acidic cpd is 40 quality % or more hour, can be more effectively with the component photographic fixing in the ink composite.
Except that agglutinant, treatment solution preferably also contains at least one in the group of selecting free water and water-miscible organic solvent composition.The details of water-miscible organic solvent is identical with those details in the ink composite, and embodiment preferred is also identical.
In the scope of not damaging effect of the present invention, treatment solution can also comprise one or more other additives.The instance of said other additive comprises known additives, like anti-siccative (wetting agent), anti-decolourant, emulsion stabilizer, penetration enhancer, UV light absorber, sanitas, mould inhibitor, pH regulator agent, surface tension modifier, skimmer, viscosity modifier, dispersion agent, dispersion stabilizer, inhibitor and sequestrant.
< formation method >
In formation method of the present invention, used aforementioned printing ink group of the present invention.Formation method of the present invention comprises: treatment solution applies process, and wherein, the treatment solution that will contain the component agglutinative agglutinant that makes in the ink composite is applied on the recording medium; First printing ink applies process, wherein, first ink composite that is selected from the printing ink group is applied to through ink jet method applies on the recording medium that has applied treatment solution in the process at treatment solution; Second printing ink applies process, wherein, second ink composite that is selected from the printing ink group is applied on first ink composite that first printing ink applies in the process to be applied through ink jet method; And solidification process, wherein, thereby through ink composite is solidified.Formation method of the present invention can randomly comprise one or more other processes.
In formation method of the present invention, apply process and first printing ink applies step through treatment solution, first ink composite is applied on the treatment solution that has been applied to recording medium.Then, applying step through second printing ink is applied to second ink composite on first ink composite.
Here, because first ink composite is configured to have excellent compendency, therefore can suppress at least a portion second ink composite is incorporated into the phenomenon in first ink composite, and in addition, the look that can also suppress second ink composite forms deterioration.In solidification process, irradiation active-energy radiation under the state that the phenomenon that preceding text are mentioned has been suppressed is to solidify first ink composite and to be applied to second ink composite on first ink composite.
As stated; In formation method according to the present invention; Be cured under the state that is inhibited owing to this phenomenon on the part that is superimposed upon second ink composite at first ink composite; Therefore when any two kinds of colors that are selected from Yellow ink compsn, magenta ink compositions and cyan ink composition through stack form redness, green or blue image, can improve the colorrendering quality of redness, green or blue image.
< treatment solution applies process >
Apply in the process at treatment solution, treatment solution is applied on the recording medium.
In the present invention, carry out treatment solution before the process and apply process, can improve the speed of ink-vapor recording through applying at printing ink, even and when under at a high speed, writing down, the high image of image density or resolving power still can be obtained.
Can through adopt currently known methods (as, coating process, ink jet method or immersed method) apply treatment solution.Coating process can carry out according to the known coating process that adopts scraping strip coating machine, overflow mould coating machine, Kohler coater, scraper plate coating machine, rod coater, knife coater, extrusion coating machine, counter-rotating roll coater etc.Details in the face of ink ejecting method describes down.
Applied amount to treatment solution is not done special restriction, as long as the applied amount of treatment solution is enough to make the ink composite aggegation, but the applied amount of treatment solution can make preferably that the applied amount of agglutinant is 0.1g/m
2Or bigger amount.Particularly, the applied amount of agglutinant is preferably 0.1g/m
2To 1.0g/m
2, 0.2g/m more preferably
2To 0.8g/m
2Applied amount at agglutinant is 0.1g/m
2Or when bigger, can advantageously carry out the aggegation of ink composite.Consider that from avoiding the too high angle of glossiness the applied amount of preferred agglutinant is 1.0g/m
2Or it is littler.
In the present invention, preferably, after being applied to treatment solution on the recording medium and before applying ink composite, also carry out the heat drying process, in said heat drying process, make the treatment solution that is applied on the recording medium dry through heating.Through applying step at printing ink, can realize excellent printing ink tint permanence (as suppressing seepage), and can write down colour density and the excellent visual image of tone before in advance with the treatment solution heat drying.
Can adopt known heating unit (like, well heater), utilize drying machine etc. the air blast function blowing device or make up the two and the device that obtains carries out heat drying.For example, adopt well heater etc. to be applied with the method, the method that adopts infrared heater to heat of method, the recording medium top blast warm braw that on it, is applied with treatment solution or hot blast of back side heating of the recording medium face of treatment solution from it; And other method all is suitable for.Can heat through two or more the combination in these methods.
< first printing ink applies process >
Apply in the process at first printing ink, first ink composite that is selected from aforementioned printing ink group is applied to through ink ejecting method applies on the recording medium that has applied treatment solution in the process at treatment solution.
Therefore through this process, treatment solution contacts with first ink composite, and the component aggegation in first ink composite makes the image fixing that is formed by first ink composite on recording medium.
Ink jet method is not done special qualification; And can be the method for any known; As; Adopt electrostatic attraction carry out ink-jet electric charge control method, utilize the oscillation pressure of piezoelectric element dripping method as required (pressure pulse method), carry out the acoustic control ink jet method of ink-jet and adopt through the radiation pressure that has produced with the acoustic beam irradiation printing ink that comes by electrical signal conversion through heating printing ink hot ink-jet (BUBBLEJET, the registered trademark) method that the pressure that produced carries out ink-jet of bubbling.The scope of ink ejecting method can comprise: the method for wherein spraying a large amount of small volume drops (being called " photograph printing ink (photoink) ") of the low printing ink of concentration; Wherein adopt have substantially the same tone but the multiple inks of different densities to improve the method for picture quality; And the method for wherein using water white transparency printing ink.
The ink gun that in ink ejecting method, uses can adopt on-demand system or continuous system.The specific examples of injection system comprises: dynamo-electric conversion system (for example, single chamber type, dual-chamber type, deflection type (bender type), piston-type, shear mode (share mode) type, share wall type etc.); Electric heating conversion system (for example, hot inkjet type, " BUBBLE JET " (registered trademark) type etc.); Electrostatic attraction system (for example, electric field controls type, narrow slit ejection-type etc.); And discharge system (for example, spark ejection-type etc.).Can use in the above-mentioned injection system any one.
Printing ink nozzle of being used for writing down through ink ejecting method etc. is not done special restriction, can select aptly according to purpose.
The instance of ink ejecting method comprises (i) pattern of shuttling back and forth, and wherein when the width of recording medium moves, carries out record with scan mode at the short series connection head of little length; And (ii) linear model, wherein use the linear head of the recording unit of arranging corresponding to a side total length of recording medium.Under linear model,, can on the whole one side of recording medium, carry out image recording, and need not move haulage system's (like print cartridge) of brachycephaly portion with scan mode through along direction movable recording media perpendicular to the recording unit orientation.Since not need to print cartridge and recording medium mobile carry out complicated scanning move control and only recording medium move, so compare with the pattern of shuttling back and forth, realized writing speed faster.Formation method of the present invention can be applied to this two kinds of patterns, but when ink jet recording method of the present invention was applied to wherein not carry out the linear model of virtual injection usually, it was tangible improving the effect of spraying tolerance range and image wear resistance.
Consider that from the angle that obtains high-definition picture the amount of the ink droplet that sprays from ink gun is preferably 0.5pL (skin liter) to 6pL, more preferably 1pL to 5pL even 2pL to 4pL more preferably.
< second printing ink applies process >
Apply in the process at second printing ink, second ink composite that is selected from aforementioned printing ink group is applied on first ink composite that first printing ink applies in the process to be applied through ink ejecting method.
In this process, form secondary color (red, blue or green) image through on first ink composite, applying second ink composite.
Consider from the angle of high speed imaging, apply first ink composite the process and preferably will lack to apply the time period that applies second ink composite in the step at second printing ink from applying at first printing ink.
In the present invention; Because at least a portion that can suppress second ink composite is incorporated in first ink composite, therefore can applies and apply first ink composite to the second printing ink the process and apply the time period that applies second ink composite in the step and be set to (for example) 200 milliseconds or shorter (preferred 150 milliseconds or shorter) from first printing ink.
The preferred embodiment that second printing ink applies ink ejecting method in the step and first printing ink apply identical in the step.
< heat drying process >
Formation method of the present invention after second printing ink applies process and before solidification process, thereby preferably include through applying the heat drying process that ink image that ink composite forms heats at least a portion solvent of removing in the ink composite.Handle through carrying out heat drying, can form image through the curing schedule that carries out subsequently with excellent adhesion and erasibility.
Heating means are not done special restriction, and its preferred examples comprises the non-contact type drying means, like the method through heat generating components (like the nichrome wire well heater) heating, blast the method for warm braw or hot blast and the method through heating such as halogen lamp, ir lamps.
< solidification process >
In solidification process, through being applied with the recording medium of ink composite, thereby solidify said ink composite (first ink composite and second ink composite) with the active-energy radiation irradiation.
Here, employed active-energy radiating instance comprises alpha-ray, gamma-rays, electron beam, X ray, ultraviolet ray, visible light and infrared light.
In curing schedule, utilize (for example) from the uviolizing of uv irradiating lamp through applying the ink image that ink composite forms.By this way, can solidify monomer component (water-soluble polymerizable compound) in the image reliably.At this moment, arrange that the uv irradiating lamp makes its recording surface towards recording medium, and shine whole recording surface to solidify entire image.The light source that is used for the irradiation of active-energy radiating is not limited to the uv irradiating lamp, can adopt halogen lamp, high voltage mercury lamp, laser, LED, electron beam illuminating device etc.
Solidification process can carry out before or after the heat drying process, as long as it is after second printing ink applies process.Solidification process can not only carry out but also after the heat drying process, carry out before the heat drying process.
Active-energy radiating illuminate condition is not done special restriction, as long as can water-soluble polymerizable compound solidified through polymerization.Active-energy radiating wavelength can (for example) be 200nm to 600nm preferably, 300nm to 450nm more preferably, and 350nm to 420nm more preferably.
Active-energy radiating work output is preferably 5000mJ/cm
2Or littler, 10mJ/cm more preferably
2To 4000mJ/cm
2, and even 20mJ/cm more preferably
2To 3000mJ/cm
2
-recording medium-
In formation method of the present invention, with image recording on recording medium.
Recording medium is not done special restriction, and it can be the general printing of cellulose family that is used for general offset printing etc., like so-called high quality paper, White Board or enamelled paper.When using aqueous ink on the general printing of cellulose family, to carry out image recording through common ink ejecting method, the absorption of printing ink is with dry relatively slow, and coloured material moves easily after applying printing ink, and picture quality is tended to descend.On the contrary, according to the formation method that uses printing ink group of the present invention, can when suppressing the coloured material migration, realize having the high quality graphic record of excellent color density and tone.
Recording medium can be the commercially available prod; And the example comprises high quality paper (A), SHIRAOI (trade(brand)name) that makes like the OK PRINCE HIGH-QUALITY (trade(brand)name) that made by Oji Paper Co., Ltd., by Nippon Paper Industries Co., Ltd. and the NEW NPI HIGH-QUALITY (trade(brand)name) that is made by Nippon Paper Industries Co., Ltd.; The White Board of lightweight is like OKEVER LIGHT COAT (trade(brand)name) that is made by Oji Paper Co., Ltd. and the AURORA S (trade(brand)name) that is made by Nippon Paper Industries Co., Ltd.; The White Board of lightweight (A3) is like OK COAT L (trade(brand)name) that is made by Oji Paper Co., Ltd. and the AURORA L (trade(brand)name) that is made by Nippon Paper Industries Co., Ltd.; White Board (A2, B2), like OK TOPCOAT+ (trade(brand)name) that makes by OjiPaper Co., Ltd. and the AURORA COAT (trade(brand)name) that makes by Nippon PaperIndustries Co., Ltd.; And enamelled paper (A1), like the OK KINFUJI+ (trade(brand)name) that makes by Oji Paper Co., Ltd. with by the TOKUBISHI ART (trade(brand)name) of Mitsubishi Papers Mills manufactured.Can also use polytype ink-vapor recording to use sensitized paper.
In the middle of aforementioned recording medium, suppress the angle of effect height and colour density and the better high quality graphic of tone from the migration that obtains coloured material and consider the preferred 0.05mL/m of absorption coerfficient Ka of recording medium
2Ms
1/2To 0.5mL/m
2Ms
1/2, more preferably 0.1mL/m
2Ms
1/2To 0.4mL/m
2Ms
1/2, more preferably 0.2mL/m also
2Ms
1/2To 0.3mL/m
2Ms
1/2
Absorption coerfficient Ka has and the identical meaning of absorption coerfficient described in the JAPAN TAPPI paper pulp TP No.51:2000 (being published by Japan Technical Association of the Pulp and Paper Industry), and its disclosure is incorporated this paper into way of reference.Particularly; Difference between water transfer amount when being 100ms from the duration of contact of using autoscan liquid-absorbent appearance KM500WIN (trade(brand)name is made by Kumagai RikiKogyo Co., Ltd.) to measure and the water transfer amount when being 900ms duration of contact is calculated absorption coerfficient Ka.
In the middle of recording medium, be preferred for the so-called White Board in general offset printing etc.Through coating being applied to the surface of not doing the common high quality paper of surface-treated cellulose family and neutralizations such as paper being obtained White Board to form coating above that.In common aqueous jet imaging, White Board might cause the problem of quality aspect, like image glossiness or erasibility.Yet, in ink jet recording method of the present invention, can reduce uneven glossiness, and can obtain glossiness and the excellent image of erasibility.Particularly, the preferred use has body paper and the White Board that contains the coating of kaolin and/or Calcium hydrogen carbonate.More specifically, the more preferably White Board of the White Board of enamelled paper, White Board, lightweight or utmost point lightweight.
< ink-jet recording device >
Next, in conjunction with Fig. 1 the instance of the ink-jet recording device that is advantageously used in formation method of the present invention is described.Fig. 1 is the synoptic diagram that the structure example of whole ink-jet recording device is shown.
As shown in Figure 1, this ink-jet recording device comprises along the throughput direction (direction of arrow shown in this figure) of recording medium in order: treatment solution applies portion 12, and it has the treatment solution splash head 12S of inject process liquid; Treatment solution drying zone 13, it has the heating unit (not shown) of the dry treatment solution that is applied; Spray the ink-jet portion 14 of various ink composites; And the ink setting district 15 of the dry ink composite that is sprayed.In addition, the uviolizing portion 16 that has a uv irradiating lamp 16S is arranged on the downstream side in ink setting district 15 along the throughput direction of recording medium.
The recording medium that has been provided to ink-jet recording device is transported to treatment solution by conveying roller from sheet feed section and applies portion 12; Be transported to treatment solution drying zone 13 then; Be transported to ink-jet portion 14 then; Be transported to ink setting district 15 then, be transported to uviolizing portion 16 then, in collection portion, collect then with the accumulation mode.Sheet feed section is supplied recording medium paper from the box that is mounted with recording medium.Can carry out the conveying of recording medium through the method or the method except the method for using conveying roller of use conveying roller, and the instance of other method comprises the platform conveying method of the cylinder conveying method, band conveying method or the usage platform that use cylinder shape parts.
In the middle of set a plurality of conveying rollers, at least one roller can be the driving roll that transmits the power that is produced by the motor (not shown) in ink-jet recording device.Through using motor to rotate this driving roll, recording medium is carried with predetermined operational throughput along predetermined direction with constant rate of speed.
Treatment solution applies portion 12 and comprises treatment solution splash head 12S, and it has the storage tank of treatment solution to be connected with wherein storing.Treatment solution splash head 12S inject process liquid from the record surface of record-oriented medium and the nozzle that is provided with makes the drop of treatment solution to be applied on the recording medium.Apply employed method in the portion 12 at treatment solution and be not limited to form with nozzle, can also be to use the coating process of coating roll from the method that shower nozzle sprays.According to coating process, treatment solution can easily be applied to the almost whole surface of recording medium, comprises the image section that will be applied ink droplet by the ink-jet portion 14 that is arranged on the downstream side.In order to make the thickness that is applied to the treatment solution on the recording medium even; Can adopt the method for utilizing air knife, maybe can adopt such method: between these parts and recording medium, provide and the corresponding gap of the treatment solution of predetermined amount thereby the parts with acute angle are set.
Treatment solution drying zone 13 is arranged on the downstream side that treatment solution applies portion 12 along the throughput direction of recording medium.Treatment solution drying zone 13 can comprise: known heating unit, like well heater; Air-blast device is like drying machine; Or these devices make up the device that obtains.Heating unit can (for example) utilize following method: wherein heat generating components (like well heater) is arranged on treatment solution with recording medium and (for example applies on the relative side of face one side; Under the situation of automatic transport recording medium, heat generating components can be provided with the below that is placed with recording medium above that and carries the transfer mechanism of this recording medium) method; The treatment solution that wherein warm braw or hot blast is applied to recording medium applies the method for face; Or the heating means of use ir heaters.These methods can be used with the mode of two or more combinations.
Because the surface temperature of recording medium can be according to variations such as the type (material, thickness etc.) of recording medium and envrionment temperatures; Therefore preferably; The member that the measurement section of survey record dielectric surface temperature is provided and is used for measured recording medium surface temperature value is fed back to heating control section, temperature controllable when forming the treatment solution applied layer thus.The measurement section that is used for survey record dielectric surface temperature is preferably contact-type or non-contact thermometer.
Can use removal of solvents roller etc. to remove desolvates.Perhaps, also available method of wherein from recording medium, removing excessive solvent through air knife.
Ink-jet portion 14 is arranged on the downstream side of treatment solution drying zone 13 along the throughput direction of recording medium.
Ink-jet portion 14 comprises ink gun 30A, 30B, 30C and 30D, their be connected with the ink reservoir of storing black (K), cyan (C), magenta (M) and yellow (Y) ink composite respectively (corresponding relation between ink gun and the ink composite are described below).Each ink reservoir (not shown) is being stored the ink composite of corresponding color, and when carrying out image recording, as required ink composite is supplied to the corresponding ink gun in the middle of ink gun 30A, 30B, 30C and the 30D.
Corresponding relation between ink gun and the ink composite is not done special restriction, be connected with the ink gun that on throughput direction, is positioned at the place, ink gun downstream side that is connected with the reservoir of storing first ink composite as long as store the reservoir of second ink composite.
Consider that from the angle of the colorrendering quality effect that more effectively shows secondary color of the present invention the reservoir that is used to store first ink composite preferably is connected with two adjacent ink guns with the reservoir that is used to store second ink composite.Preferred embodiment specific examples comprise: the reservoir that (1) wherein is used to store first ink composite is connected and is used to store the embodiment that the reservoir of second ink composite is connected with ink gun 30B with ink gun 30A; (2) reservoir that wherein is used to store first ink composite is connected and is used to store the embodiment that the reservoir of second ink composite is connected with ink gun 30C with ink gun 30B; And (3) reservoir of wherein being used to store first ink composite is connected and is used to store the embodiment that the reservoir of second ink composite is connected with ink gun 30D with ink gun 30C.
In addition, ink-jet portion 14 can be between downstream side, ink gun 30A and the ink gun 30B of the upstream side of ink gun 30A, ink gun 30D, between ink gun 30B and the ink gun 30C and at least one place between ink gun 30C and the ink gun 30D is provided with other ink gun.As stated, except that the ink-jet portion 14 with 4 ink guns as shown in Figure 1, can be with ink-jet portion as said ink-jet portion with 5 of being provided with along throughput direction or more a plurality of ink guns.
In addition in this case, storing the reservoir of second ink composite connects with the ink gun at the place, downstream side that on throughput direction, is positioned at the ink gun that is connected with the reservoir of storing first ink composite.
Each is all fronts head (full-1ine head) forms for treatment solution splash head 12S and ink gun 30A, 30B, 30C and 30D, and wherein a plurality of jet orifices (nozzle) are arranged along the dominant record width of waiting to be recorded in the image on the recording medium.In this form; Compare with using when scanning, can on recording medium, carry out image recording at a high speed along the reciprocating short length of width (the direction on the recording medium face) of the recording medium tandem type record that head writes down that shuttles back and forth perpendicular to recording medium transporting direction.In the present invention; Can adopt above-mentioned tandem type recording method or the recording method that can write down with higher relatively speed, as can with run-down promptly form the single pass (single-pass) of line thus mode is sprayed the single pass system that writes down along main scanning direction.In image recording process of the present invention,, also can obtain to have the high quality graphic of high reproducibility even in the single pass system.
Here, treatment solution splash head 12S has identical structure respectively with ink gun 30A, 30B, 30C and 30D.
The applied amount of treatment solution and the applied amount of ink composite are preferably regulated as required.For example, can be according to the amount of the type change treatment solution of recording medium, thus the character of regulating formed agglomeration when treatment solution and ink composite mixing, like visco-elasticity.
Ink-jet recording device can also comprise heating unit on the transport way from sheet feed section 20 to collection portion 30, so that recording medium is carried out heat treated.For example, through in desired location (like, the upstream side of treatment solution drying zone 13 or between ink-jet portion 14 and ink setting district 15) heating unit being provided, it is temperature required that the temperature of recording medium is risen to, thereby carry out drying and photographic fixing effectively.
Embodiment
Further describe the present invention below in conjunction with following examples, but should be understood that the present invention is confined to these embodiment never in any form.Unless otherwise, " part " and " % " is benchmark with the quality.
[synthetic example]
" water soluble resin dispersion agent P-1's is synthetic "
According to following operation synthesizing water-solubility pitch dispersant P-1.
Prepare monomer through mixed methyl vinylformic acid (172 parts), methylacrylic acid benzyl ester (828 parts) and Virahol (375 parts) and supply with compsn.Through mixing 2, two (2-methylbutyronitrile) (22.05 parts) of 2-azo and Virahol (187.5 parts) prepare initiator and supply with compsn.
The mixture of monomer being supplied with compsn and initiator supply compsn dropwise was added into the Virahol (187.5 parts) that under nitrogen atmosphere, is heated to 80 ℃ in 2 hours.After dropwise adding end, mixture was further kept 4 hours down at 80 ℃, be cooled to 25 ℃ subsequently.
After the cooling, removal of solvent under reduced pressure with obtain weight-average molecular weight be about 30000 and acid number be the water soluble resin dispersion agent P-1 (water soluble resin) of 112mgKOH/g.
" preparation of magenta ink compositions (M1) "
< preparation of magenta pigment dispersion-s A >
The water soluble resin dispersion agent P-1 (150 parts) that preceding text are obtained neutralizes with preparation water soluble resin aqueous dispersant with potassium hydroxide aqueous solution, make that the pH after the neutralization is 9, and the concentration of water soluble resin dispersion agent is 25 quality %.
Water soluble resin aqueous dispersant (58.3 parts), pigment red 122 (magenta pigment) (48.6 parts), water (144 parts) and the dipropylene glycol (75 parts) of gained mixed in ball mill (diameter is the zirconium oxide bead of 0.1mm Ф) and disperseed 4 hours, to obtain the dispersion-s N1 (uncrosslinked dispersion-s) that pigment concentration is 15% resin-coated magenta pigment particles.
DENACOL EX-321 (trade(brand)name is by the linking agent of Nagase Chemtex manufactured) (0.4 part) is added among the dispersion-s N1 (136 parts), reacted 6.5 hours down at 50 ℃ subsequently, and mixture is cooled to 25 ℃ to obtain crosslinked dispersion-s.With resulting crosslinked dispersion-s with ultra filtration filter (classification molecular weight 50,000, Q0500076EULTRAFILTER; Trade(brand)name is made by ADVANTEC) carry out ultrafiltration, subsequent purificn; And process the pigment concentration of 15 quality %, obtain magenta pigment dispersion-s A thus.
< preparation of magenta ink compositions (M1) >
Following composition is mixed, filter, and filter (Millipore makes for pvdf membrane, aperture 5 μ m) to obtain magenta ink compositions (M1) through strainer through glass filter (ADVANTEC makes for GS-25, trade(brand)name).
The composition of magenta ink compositions (M1)
-magenta pigment dispersion-s A:35.3 part
Polymerizable compound 2:21 part that-hereinafter provides
-OLFINE E1010 (trade(brand)name, tensio-active agent are made by Nissin Chemical Industry Co., Ltd.): 1 part
-IRGACURE 2959 (trade(brand)name, Photoepolymerizationinitiater initiater are made by BASF Japan): 3 parts
-surplus is that ion exchanged water makes and adds up to 100 parts
Here, polymerizable compound 2 is the compounds that are described below synthetic and have the structure that hereinafter provides.
-polymerizable compound 2 synthetic-
4 of 40.0g (182mmol) packs in the 1L three-necked flask that is equipped with whisking appliance; 7; 10-trioxa-1; 13-tridecane diamines, 37.8g (450mmol) sodium hydrogencarbonate, 100g water and 300g THF, and under condition of ice bath wherein dropwise add the acrylate chloride of 35.2g (389mmol) 20 minutes introversions.After dropwise adding end, mixture was at room temperature stirred 5 hours, and from the reaction mixture of gained, remove THF through reduction vaporization.Then, with 200ml ethyl acetate extraction water layer 4 times, and with the organic layer of gained with dried over mgso and filter, subsequently through solvent removed by evaporation at reduced pressure, thereby obtain the solid of the required polymerizable compound 2 of 35.0g (107mmol, productive rate 59%).The A value of this polymerizable compound 2 is 164.2.
In " the equal particle diameter of body [nm] " hurdle of table 1 and table 2, provided the equal particle diameter of particulate body (second particle) contained in the magenta ink compositions (M1).Use NANOTRAC size distribution analyser UPA-EX150 (trade(brand)name; Make by Nikkiso Co., Ltd.), through the equal particle diameter of dynamic light scattering method measuring body (second particle).
In " P (%) " hurdle of table 1 and table 2, provided the content (unit: quality %) of pigment red 122 (magenta pigment) with respect to magenta ink compositions (M1) total amount.
Water soluble resin crosslinked in the magenta ink compositions (M1) and the mass ratio of magenta pigment [quality of the quality/pigment red 122 of crosslinked water soluble resin (magenta pigment)] in " D/P " hurdle of table 1 and table 2, have been provided.
In " crosslinked back acid number [mgKOH/g] " hurdle of table 1 and table 2, provided the acid number [mgKOH/g] of the water soluble resin dispersion agent P-1 (water soluble resin) after crosslinked in the magenta ink compositions (M1).
" preparation of magenta ink compositions (M2 to M10 and M12) "
Through with the preparation of magenta pigment dispersion-s A in the method similar methods come to prepare respectively the magenta pigment dispersion-s that is used for magenta ink compositions M2 to M10 and M12.Yet; Change amount and the jitter time of dispersion agent P-1, potassium hydroxide aqueous solution and DENACOLEX-321 as required; Thereby the mass ratio [quality of the quality/magenta pigment of crosslinked water soluble resin] that provides in table 1 and the table 2, acid number and the equal particle diameter of body (for the magenta pigment dispersion-s that is used for magenta ink compositions M10 and M12, not using DENACOL EX-321) after crosslinked are provided.Then; With basically with magenta ink compositions (M1) in identical mode prepare every kind of magenta ink compositions (M2 to M10; M12); Difference is to use respectively the magenta pigment dispersion-s that is used for magenta ink compositions M2 to M10 and M12, and in every kind of magenta ink compositions M2 to M10 and M12, thereby the magenta pigment content that the amount of change magenta pigment dispersion-s obtains providing in table 1 and the table 2.
For magenta ink compositions M10 and M12, the magenta pigment dispersion-s is not carried out crosslinked, and to uncrosslinked dispersion-s carry out ultrafiltration with the preparation ink composite.
" preparation of magenta ink compositions (M11) "
With with magenta ink compositions M1 in identical mode preparation red ink composition M11; Difference is pearl used in the ball mill is changed over the zirconium oxide bead that diameter is 0.05mm Ф, and the adjustment jitter time is until obtaining the equal particle diameter of required body.
" preparation of Yellow ink compsn (Y1) "
< preparation of yellow pigment dispersion B >
The water soluble resin dispersion agent P-1 (150 parts) that preceding text are obtained neutralizes with preparation water soluble resin aqueous dispersant with potassium hydroxide aqueous solution, make that the pH after the neutralization is 9, and the concentration of water soluble resin dispersion agent is 25 quality %.
Water soluble resin aqueous dispersant (116.6 parts), Pigment Yellow 73 74 (yellow ultramarine) (48.6 parts), water (128.8 parts) and the dipropylene glycol (30 parts) of gained mixed in ball mill (diameter is the zirconium oxide bead of 0.1mm Ф) and disperse until obtaining the required equal particle diameter of body, is 15% resin-coated yellow ultramarine particulate dispersion-s N2 (uncrosslinked dispersion-s) thereby obtain pigment concentration.
DENACOL EX-321 (by the linking agent of Nagase Chemtex manufactured) (0.9 part) is added among the dispersion-s N2 (136 parts), reacted 6.5 hours down at 50 ℃ subsequently, and mixture is cooled to 25 ℃ to obtain crosslinked dispersion-s.With resulting crosslinked dispersion-s with ultra filtration filter (classification molecular weight 50,000, Q0500076EULTRAFILTER; Trade(brand)name is made by ADVANTEC) carry out ultrafiltration, subsequent purificn; Then pigment concentration is adjusted into 15 quality %, obtains yellow pigment dispersion B thus.
< preparation of Yellow ink compsn (Y1) >
Following composition is mixed, filter, and filter through strainer (pvdf membrane, aperture 5 μ m are made by Millipore) subsequently, thereby obtain Yellow ink compsn (Y1) through glass filter (GS-25, trade(brand)name are made by ADVANTEC).
< composition of Yellow ink compsn (Y1) >
-yellow pigment dispersion B:25.3 part
Polymerizable compound 2:21 part that-preceding text provide
-OLFINE E1010 (trade(brand)name, tensio-active agent are made by Nissin Chemical Industry Co., Ltd.): 1 part
-IRGACURE 2959 (trade(brand)name, Photoepolymerizationinitiater initiater are made by BASF Japan): 3 parts
-surplus is that ion exchanged water makes and adds up to 100 parts
In " the equal particle diameter of body [nm] " hurdle of table 2 and table 3, provided the equal particle diameter of particulate body (second particle) contained in the Yellow ink compsn (Y1).Use NANOTRAC particle size distribution analysis appearance UPA-EX150 (trade(brand)name; Make by Nikkiso Co., Ltd.), through the equal particle diameter of dynamic light scattering method measuring body (second particle).
In " P (%) " hurdle of table 2 and table 3, provided the content (unit: quality %) of Pigment Yellow 73 74 (yellow ultramarine) with respect to Yellow ink compsn (Y1) total amount.
The water soluble resin crosslinked in the Yellow ink compsn (Y1) and the mass ratio of yellow ultramarine [quality of the quality/Pigment Yellow 73 74 (yellow ultramarine) of crosslinked water soluble resin] in " D/P " hurdle of table 2 and table 3, have been provided.
In " acid number after crosslinked [mgKOH/g] " hurdle of table 2 and table 3, provided the acid number [mgKOH/g] of crosslinked back water soluble resin dispersion agent P-1 (water soluble resin) in the Yellow ink compsn (Y1).
" preparation of Yellow ink compsn (Y2 to Y9) "
Through with the preparation of yellow pigment dispersion B in the method similar methods prepare each yellow pigment dispersion that is used for Yellow ink compsn Y2 to Y9 respectively.Yet; Change amount and the jitter time of dispersion agent P-1, potassium hydroxide aqueous solution and DENACOL EX-321 as required; Thereby the mass ratio [quality of the quality/yellow ultramarine of crosslinked water soluble resin] that provides in table 2 and the table 3, crosslinked back acid number and the equal particle diameter of body (for each yellow pigment dispersion that is used for Yellow ink compsn Y2, Y4, Y6 and Y9, not using DENACOLEX-321) are provided.Then; With basically with Yellow ink compsn (Y1) in identical mode prepare each Yellow ink compsn (Y2 to Y9); Difference is to use respectively the yellow pigment dispersion that is used for Yellow ink compsn Y2 to Y9; And in every kind of Yellow ink compsn Y2 to Y9, thereby the yellow ultramarine content that the amount of change yellow pigment dispersion obtains providing in table 2 and the table 3.
For Yellow ink compsn Y2, Y4, Y6 and Y9, yellow pigment dispersion is not carried out crosslinked, and to uncrosslinked dispersion-s carry out ultrafiltration with the preparation ink composite.
" preparation of cyan ink composition (C1) "
< preparation of green pigment dispersion-s C >
The water soluble resin dispersion agent P-1 (150 parts) that preceding text are obtained neutralizes with preparation water soluble resin aqueous dispersant with potassium hydroxide aqueous solution, make that the pH after the neutralization is 9, and the concentration of water soluble resin dispersion agent is 25 quality %.
Water soluble resin aqueous dispersant (97.2 parts), pigment Blue 15 with gained: 3 (green pigments) (48.6 parts), water (78.2 parts) and dipropylene glycol (100 parts) mix in ball mill (diameter is the zirconium oxide bead of 0.1mm Ф) and disperse until obtaining the required equal particle diameter of body, are 15% resin-coated green pigment particulate dispersion-s N3 (uncrosslinked dispersion-s) thereby obtain pigment concentration.
DENACOL EX-321 (trade(brand)name is by the linking agent of Nagase Chemtex manufactured) (1 part) is added among the dispersion-s N3 (136 parts), reacted 6.5 hours down at 50 ℃ subsequently, and mixture is cooled to 25 ℃ to obtain crosslinked dispersion-s.With resulting crosslinked dispersion-s with ultra filtration filter (classification molecular weight 50,000, Q0500076EULTRAFILTER; Trade(brand)name is made by ADVANTEC) carry out ultrafiltration, subsequent purificn; Then pigment concentration is adjusted into 15 quality %, obtains green pigment dispersion-s C thus.
< preparation of cyan ink composition (C1) >
Following composition is mixed, filter, and filter, thereby obtain cyan ink composition (C1) through strainer (pvdf membrane, aperture 5 μ m are made by Millipore) through glass filter (GS-25, trade(brand)name are made by ADVANTEC).
The composition of cyan ink composition (C1)
-green pigment dispersion-s C:16 part
Polymerizable compound 2:21 part that-preceding text provide
-OLFINE E1010 (trade(brand)name, tensio-active agent are made by Nissin Chemical Industry Co., Ltd.): 1 part
-IRGACURE 2959 (trade(brand)name, Photoepolymerizationinitiater initiater are made by BASF Japan): 3 parts
-surplus is that ion exchanged water makes and adds up to 100 parts
In " the equal particle diameter of body [nm] " hurdle of table 1 and table 3, provided the contained equal particle diameter of particulate body (second particle) in the cyan ink composition (C 1).Use NANOTRAC size distribution analyser UPA-EX150 (trade(brand)name; Make by Nikkiso Co., Ltd.), through the equal particle diameter of dynamic light scattering method measuring body (second particle).
In " P (%) " hurdle of table 1 and table 3, provided pigment Blue 15: 3 (green pigments) are with respect to the content (unit: quality %) of cyan ink composition (C1) total amount.
Water soluble resin crosslinked in the cyan ink composition (C1) and the mass ratio of green pigment [quality/pigment Blue 15 of crosslinked water soluble resin: the quality of 3 (green pigments)] in " D/P " hurdle of table 1 and table 3, have been provided.
In " acid number after crosslinked [mgKOH/g] " hurdle of table 1 and table 3, provided the acid number [mgKOH/g] of crosslinked back water soluble resin dispersion agent P-1 (water soluble resin) in the cyan ink composition (C1).
" preparation of cyan ink composition (C2 to C17) "
Through with the preparation of green pigment dispersion-s C in the method similar methods prepare each the green pigment dispersion-s that is used for cyan ink composition C2 to C 17.Yet; Change amount and the jitter time of dispersion agent P-1, potassium hydroxide aqueous solution and DENACOL EX-321 as required; Thereby the mass ratio [quality of the quality/green pigment of crosslinked water soluble resin] that provides in table 1 and the table 3, crosslinked back acid number and the equal particle diameter of body (for each the green pigment dispersion-s that is used for cyan ink composition C6, C7 and C 13, not using DENACOLEX-321) are provided.Then; With basically with cyan ink composition (C1) in identical mode prepare every kind of cyan ink composition (C2 to C17); Difference is to use respectively the green pigment dispersion-s that is used for cyan ink composition C2 to C17; And in every kind of cyan ink composition C2 to C17, thereby the green pigment content that the amount of change green pigment dispersion-s obtains providing in table 1 and the table 3.
For cyan ink composition C6, C7 and C13, the green pigment dispersion-s is not carried out crosslinked, and to uncrosslinked dispersion-s carry out ultrafiltration with the preparation ink composite.
" preparation of black ink composition (K1) "
< preparation of black point prose style free from parallelism K >
The water soluble resin dispersion agent P-1 (150 parts) that preceding text are obtained neutralizes with preparation water soluble resin aqueous dispersant with potassium hydroxide aqueous solution, make that the pH after the neutralization is 9, and the concentration of water soluble resin dispersion agent is 25 quality %.
Water soluble resin aqueous dispersant (97.2 parts), charcoal blacks (NIPEX170-IQ with gained; Trade(brand)name; Make by Degussa) (48.6 parts), water (78.2 parts) mixes in ball mill (diameter is the zirconium oxide bead of 0.1mm Ф) with dipropylene glycol (100 parts) and disperse until the required equal particle diameter of body of acquisition, thereby obtain the dispersion-s N4 (uncrosslinked dispersion-s) that pigment concentration is 15% resin-coated black pigment particles.
DENACOL EX-321 (by the linking agent of Nagase Chemtex manufactured) (1 part) is added among the dispersion-s N4 (136 parts), reacted 6.5 hours down at 50 ℃ subsequently, and mixture is cooled to 25 ℃ to obtain crosslinked dispersion-s.With resulting crosslinked dispersion-s with ultra filtration filter (classification molecular weight 50,000, Q0500076E ULTRAFILTER; Trade(brand)name is made by ADVANTEC) carry out ultrafiltration, subsequent purificn; Subsequently pigment concentration is adjusted into 15 quality %, obtains black pigment dispersion-s K thus.
< preparation of black ink composition (K1) >
Following composition is mixed, filter (GS-25, trade(brand)name are made by ADVANTEC), and filter, thereby obtain black ink composition (K1) through strainer (pvdf membrane, aperture 5 μ m are made by Millipore) through glass filter.
The composition of black ink composition (K1)
-black pigment dispersion-s K:23 part
Polymerizable compound 2:21 part that-preceding text provide
-OLFINE E1010 (tensio-active agent is made by Nissin Chemical Industry Co., Ltd.): 1 part
-IRGACURE 2959 (trade(brand)name, Photoepolymerizationinitiater initiater are made by BASF Japan): 3 parts
-surplus is that ion exchanged water makes and adds up to 100 parts
" preparation of treatment solution "
The component of mixing following composition is with the preparation treatment solution.
The treatment solution of gained has the viscosity of 2.5mPa.s, the surface tension of 40mN/m and 1.0 pH (25 ± 1 ℃).
Here, surface tension is measured with automatic surface tonometer CBVP-Z (trade(brand)name is made by KyowaInterface Science Co., Ltd.), and viscosity is measured with DV-III ULTRA CP (trade(brand)name is made by Brookfield Engineering).PH measures with PH METERHM-30R (trade(brand)name is by the DKK-TOA manufactured).
" composition of treatment solution "
-propanedioic acid (making): 25% by Wako Pure Chemical Industries ltd
-methyl carbitol (making): 20.0% by Wako Pure Chemical Industries ltd
-EMULGEN P109 (trade(brand)name, nonionogenic tenside is by the Kao manufactured): 1.0%
-surplus is that ion exchanged water makes and adds up to 100 parts
[Test Example 101 to 116,201 to 219 and 301 to 316]
" printing ink group "
Preparation comprises each printing ink group of the combination of one of one of one of magenta ink compositions M1 to M12, Yellow ink compsn Y1 to Y9, cyan ink composition C1 to C17, black ink composition K1 and treatment solution.
" image formation "
Use the printing ink group that is obtained, the double-colored printing ink (printing ink 1 and printing ink 2) that provides through table 1 to table 3 forms image.
Particularly; The printing ink 1 that provides in the use table 1 forms blue image (Test Example 101 to 116) with printing ink 2; The printing ink 1 that provides in the use table 2 forms red image (Test Example 201 to 219) with printing ink 2, and the printing ink 1 that provides in the use table 3 forms green image (Test Example 301 to 316) with printing ink 2.
In table 1 to table 3, " printing ink 1 " representative is applied to the printing ink on the recording medium as first ink composite, and " printing ink 2 " representative is applied to the printing ink on the printing ink 1 as second ink composite.
The formation of each image is described below and carries out.
At first, as shown in Figure 1, prepare ink discharge device, it comprises that throughput direction (direction of arrow among Fig. 1) along recording medium is arranged in order: the treatment solution with treatment solution splash head 12S of inject process liquid applies portion 12; The treatment solution drying zone 13 of the dry treatment solution that is applied; Spray the ink-jet portion 14 of multiple water color ink; The ink setting district 15 of the dry water color ink that is sprayed; With uviolizing portion 16 with ultraviolet radiator 16S that can irradiation ultraviolet radiation.
Though do not show; But thereby the record surface side supply dry wind that treatment solution drying zone 13 has at recording medium carries out the exsiccant gas blower; And the ir heaters with the non-recording surface side that is positioned at recording medium, and said treatment solution drying zone 13 is configured to the treatment solution that is applied on the recording medium is carried out drying.In ink-jet portion 14, ink gun 30A, ink gun 30B, ink gun 30C and ink gun 30D are arranged in order along throughput direction (direction of arrow).Each ink gun is the wide all fronts head of 1200dpi/10 inch (driving frequency: 25kHz, the transfer rate of recording medium: 530mm/ second).Each ink gun sprays the printing ink of respective color, document image thus with one-pass mode when on respect to the main scanning direction of recording medium, moving.
Printing ink group (treatment solution, magenta ink compositions, Yellow ink compsn, cyan ink composition and black ink composition) is encased in respectively in the storage tank (not shown) that is connected with ink gun 30A, 30B, 30C and the 30D of the treatment solution splash head 12S of ink discharge device shown in Fig. 1 and corresponding color.
Particularly; Treatment solution is encased in the storage tank that is connected with treatment solution splash head 12S; The printing ink that provides in table 1 to the table 31 is encased in the storage tank that is connected with ink gun 30A; The printing ink that provides in table 1 to the table 32 is encased in the storage tank that is connected with ink gun 30B, and with other double-colored printing ink (printing ink of the different colours except that printing ink 1 and printing ink 2) be encased in 30C and storage tank that 30D is connected in.
As stated, the printing ink assembling is loaded onto ink discharge device, and on recording medium, writes down the linear image of solid image (solid image) and 1200dpi.
At this moment, set be applied to recording medium the processing liquid measure so that the thickness of about 1.2 μ m to be provided.
As recording medium, use " U-LITE " (trade(brand)name, the basic weight 84.9g/m that makes by Nippon Paper Industries Co., Ltd.
2) or TOKUBISHI ART DOUBLE-SIDED N PAPER (trade(brand)name) (the basic weight 104.7g/m that makes by Mitsubishi Papers Mills Ltd
2).
When document image, come inject process liquid and ink composite with the resolving power of 1200dpi * 1200dpi and the quantity of ink of every 3pL.
On main scanning direction, spray 1 breadth line, 2 breadth lines and 4 breadth lines with one-pass mode with 1200dpi, thus the record linear image.
The sample for preparing with wherein on the solid image of printing ink 1, forming the solid image of printing ink 2 comes evaluate color reproducibility and erasibility.
When image recording, treatment solution is at first sprayed on recording medium from treatment solution splash head 12S with one-pass mode.Drying is applied to the treatment solution on the recording medium in treatment solution drying zone 13, makes the 900msec of treatment solution after beginning inject process liquid that is applied on the recording medium pass through the treatment solution drying zone in the time.In treatment solution drying zone 13; The opposite side (back side) that the surface of treatment solution is arranged from the injection of recording medium; The treatment solution that the heating of use ir heaters is sprayed is so that the surface temperature of the treatment solution that sprays maintains 40 ℃ to 45 ℃; Simultaneously, use gas blower through blowing the dry amount of 120 ℃ of hot blasts to obtain to be scheduled to of different air capacities, thus dry record surface.
Subsequently, in ink-jet portion 14, printing ink 1 is ejected on the dried treatment solution from ink gun 30A, and printing ink 2 is ejected on the printing ink 1 that has sprayed from ink gun 30B.At this moment, be set at 140 milliseconds from time period of ink jet 1 to ink jet 2, thus document image.
With with the similar mode of aforesaid treatment solution drying process; The opposite side (back side) that the surface of printing ink is arranged from the injection of recording medium; Use ir heaters to heat; Simultaneously, use gas blower to be the hot blast of 5m/sec 15 seconds through blow temperature to record surface be 120 ℃, air velocity, thus in ink setting district 15 that document image is dry.
After image dried, (use metal halide lamp, by Eye Graphics manufactured, the maximum illumination wavelength: 365nm), making accumulated dose is 3J/cm through irradiating ultraviolet light in uviolizing portion 16
2Thereby, image is solidified.
" picture appraisal "
The picture appraisal of the image that carries out above-mentioned formation is described below.
Provide in evaluation result table 1 below to the table 3.
< picture quality (imaging) >
For 1 breadth line that on U-LITE, writes down as stated, 2 breadth lines and 4 breadth lines, estimate imaging according to following judgement criteria.
-judgement criteria-
1: whole lines all is uniform line.
2:1 point breadth line is uniformly, but in the some parts of 2 breadth lines and 4 breadth lines, observes line width inhomogeneous and/or broken string and/or printing ink trace.
3:1 point breadth line is uniformly, but in the four corner of 2 breadth lines and 4 breadth lines, all observes line width inhomogeneous and/or broken string and/or printing ink trace.
4: in the four corner of said line, all observe tangible line width inhomogeneous and/or broken string and printing ink trace.
< picture quality (erasibility) >
The solid image sample that makes on the TOKUBISHI ART PAPER record left standstill 72 hours under 25 ℃ of conditions with 50%RH.Then, a Unrecorded TOKUBIS HIART PAPER (hereinafter with regard to current evaluation, being called untapped sample) is placed on the solid image of sample and with 200kg/m
2Load to its repeatedly (front and back) rub and wipe 10 times.Untapped sample of visual observation and solid image, and according to following judgement criteria evaluation erasibility.
-judgement criteria-
1: do not observe the solid image deterioration after color is transferred to untapped sample and rubs wiping.
2: observe color and be transferred to untapped sample, but do not observe the solid image deterioration of rubbing after the wiping.
3: observe the solid image deterioration after color is transferred to untapped sample and rubs wiping.
4: observe color and be transferred to untapped sample, and the solid image of rubbing after the wiping comes off, thereby cause paper to expose.
< colorrendering quality >
The SPECTROSCAN that use is made by GretagMacBeth; The image that is used for the colorrendering quality evaluation to being printed on the TOKUBISHI ART PAPER carries out color measurenent, and the result is plotted on the chromaticity diagram distance with true origin on the measuring distance chromaticity diagram.Particularly, use a* value (by " a " in the equality 1 expression) and b* value (by " b " in the equality 1 expression) on the chromaticity diagram, calculate Δ E by equality 1 expression.The high more representative color reproducibility of the value of Δ E is good more.
[equality 1]
Blue judgement criteria
A：60≤ΔE
B：58≤ΔE＜60
C：56≤ΔE＜58
D：53≤ΔE＜56
E：ΔE＜53
Red judgement criteria
A：87≤ΔE
B：85≤ΔE＜87
C：83≤ΔE＜85
D：80≤ΔE＜83
E：ΔE＜80
Green judgement criteria
A：80≤ΔE
B：75≤ΔE＜80
C：73≤ΔE＜75
D：70≤ΔE＜73
E：ΔE＜70
Like table 1 to shown in the table 3; The content that uses magenta pigment wherein with respect to the total amount of magenta ink compositions be the mass ratio [quality of the quality/magenta pigment of crosslinked water soluble resin] of 4.2 quality % to 6.0 quality % and crosslinked water soluble resin and magenta pigment be 0.25 or the bigger embodiment of magenta ink compositions as first ink composite in; The erasibility of imaging and image is excellent, and the colorrendering quality of secondary color is excellent.
In addition; The content that uses green pigment wherein with respect to the total amount of cyan ink composition be the mass ratio [quality of the quality/green pigment of crosslinked water soluble resin] of 2.0 quality % to 4.0 quality % and crosslinked water soluble resin and green pigment be 0.40 or the bigger Test Example of cyan ink composition as first ink composite in; The erasibility of imaging and image is excellent, and the colorrendering quality of secondary color is excellent.
In addition; The content that uses yellow ultramarine wherein with respect to the total amount of Yellow ink compsn be the mass ratio [quality of the quality/yellow ultramarine of crosslinked water soluble resin] of 3.0 quality % to 6.0 quality % and crosslinked water soluble resin and yellow ultramarine be 0.40 or the bigger Test Example of Yellow ink compsn as first ink composite in; The erasibility of imaging and image is excellent, and the colorrendering quality of secondary color is excellent.
Exemplary of the present invention includes but not limited to following content.
< 1>a kind of printing ink group comprises: the Yellow ink compsn, and it contains resin-coated yellow ultramarine, water-soluble polymerizable compound and the water of the water soluble resin lining that yellow ultramarine wherein is crosslinked; Magenta ink compositions, it contains resin-coated magenta pigment, water-soluble polymerizable compound and the water of the water soluble resin lining that magenta pigment wherein is crosslinked; Cyan ink composition, it contains resin-coated green pigment, water-soluble polymerizable compound and the water of the water soluble resin lining that green pigment wherein is crosslinked; And treatment solution, it contains the composition agglutinative agglutinant that makes in the ink composite,
Wherein, When any two kinds of ink composites when be selected from the group of being made up of said Yellow ink compsn, magenta ink compositions and cyan ink composition through stack in form redness, green or blue image, below satisfying, Yellow ink compsn, magenta ink compsn or the cyan ink composition that is at first sprayed in the middle of these two kinds of ink composites require one in (1) to (3):
(1) when the ink composite that is at first sprayed in the middle of said two kinds of ink composites is magenta ink compositions; The content of the magenta pigment in this magenta ink compositions is 4.2 quality % to 6.0 quality % with respect to the total amount of said magenta ink compositions, and said crosslinked water soluble resin and the mass ratio (quality of the quality/magenta pigment of crosslinked water soluble resin) of said magenta pigment are 0.25 or bigger;
(2) when the ink composite that is at first sprayed in the middle of said two kinds of ink composites is cyan ink composition; The content of the green pigment in this cyan ink composition is 2.0 quality % to 4.0 quality % with respect to the total amount of said cyan ink composition, and said crosslinked water soluble resin and the mass ratio (quality of the quality/green pigment of crosslinked water soluble resin) of said green pigment are 0.40 or bigger; Perhaps
(3) when the ink composite that is at first sprayed in the middle of said two kinds of ink composites is the Yellow ink compsn; The content of the yellow ultramarine in this Yellow ink compsn is 3.0 quality % to 6.0 quality % with respect to the total amount of said Yellow ink compsn, and said crosslinked water soluble resin and the mass ratio (quality of the quality/yellow ultramarine of crosslinked water soluble resin) of said yellow ultramarine are 0.40 or bigger.
< 2>above-mentioned < 1>described printing ink group, the equal particle diameter of body that wherein is selected from least a resin-coated pigment in the group of being made up of said resin-coated yellow ultramarine, said resin-coated magenta pigment and said resin-coated green pigment is 50nm to 150nm.
< 3>the described printing ink group in above-mentioned < 1>or < 2 >, at least a ink composite that wherein is selected from the group of being made up of said Yellow ink compsn, said magenta ink compositions and said cyan ink composition further comprises Photoepolymerizationinitiater initiater.
< 4>any described printing ink group in above-mentioned < 1>to < 3 >; Wherein at least a ink composite in being selected from the group of being made up of said Yellow ink compsn, said magenta ink compositions and said cyan ink composition, said water soluble resin comprises carboxyl.
< 5>any described printing ink group in above-mentioned < 1>to < 4 >; Wherein at least a resin-coated pigment in being selected from the group of forming by said resin-coated green pigment, said resin-coated magenta pigment and said resin-coated yellow ultramarine; Said water soluble resin comprises derived from the formation unit of (methyl) vinylformic acid benzyl ester with derived from (methyl) acrylic acid formation unit at least, and the acid number behind this water soluble resin crosslinked is 55mgKOH/g to 100mgKOH/g.
< 6>any described printing ink group in above-mentioned < 1>to < 5 >, the equal particle diameter of body that wherein is selected from least a resin-coated pigment in the group of being made up of said resin-coated green pigment and said resin-coated magenta pigment is 50nm to 100nm.
< 7>any described printing ink group in above-mentioned < 1>to < 6 >, the agglutinant in the wherein said treatment solution is an acidic cpd.
< 8>any described printing ink group in above-mentioned < 1>to < 7 >; Wherein at least a ink composite in being selected from the group of forming by said Yellow ink compsn, said magenta ink compositions and said cyan ink composition; Said water-soluble polymerizable compound comprises two or more polymerizable functional groups that are selected from the group of being made up of acrylamido, methacryloyl amido, dimaleoyl imino, ethene sulfuryl and N-vinylamide base, and the ratio of the number of the said polymerizable functional group that is contained in molecular weight and the molecule is 175 or littler.
< 9>formation method of any described printing ink group in use above-mentioned < 1>to < 8 >, this method comprises:
The treatment solution that will contain the composition agglutinative agglutinant that makes in the ink composite is applied on the recording medium,
First ink composite that will be selected from said printing ink group through ink ejecting method is applied on the recording medium that is applied with said treatment solution,
Second ink composite that will be selected from said printing ink group through ink ejecting method is applied on said first ink composite that is applied on the said recording medium, and
Through the active-energy radiation irradiation has been applied with on the recording medium of said ink composite on it, thereby said ink composite is solidified.
< 10>above-mentioned < 9>described formation method, wherein said active-energy irradiation are ultraviolet ray.
The content of all public publications, patented claim and the technological standard of mentioning in the application's book all is incorporated herein by reference, and should regard as as these public publications, patented claim or technological standard specifically and independently to be incorporated herein by reference equally.
Claims (10)
1. printing ink group comprises: the Yellow ink compsn, and it contains resin-coated yellow ultramarine, water-soluble polymerizable compound and the water of the water soluble resin lining that yellow ultramarine wherein is crosslinked; Magenta ink compositions, it contains resin-coated magenta pigment, water-soluble polymerizable compound and the water of the water soluble resin lining that magenta pigment wherein is crosslinked; Cyan ink composition, it contains resin-coated green pigment, water-soluble polymerizable compound and the water of the water soluble resin lining that green pigment wherein is crosslinked; And treatment solution, it contains the composition agglutinative agglutinant that makes in the ink composite,
Wherein, When any two kinds of ink composites when be selected from the group of being made up of said Yellow ink compsn, said magenta ink compositions and said cyan ink composition through stack in form redness, green or blue image, below satisfying, Yellow ink compsn, magenta ink compositions or the cyan ink composition that is at first sprayed in the middle of these two kinds of ink composites require one in (1) to (3):
(1) when the ink composite that is at first sprayed in the middle of said two kinds of ink composites is said magenta ink compositions; The content of the said magenta pigment in this magenta ink compositions is 4.2 quality % to 6.0 quality % with respect to the total amount of said magenta ink compositions, and said crosslinked water soluble resin and the mass ratio (quality of the quality/magenta pigment of crosslinked water soluble resin) of said magenta pigment are 0.25 or bigger;
(2) when the ink composite that is at first sprayed in the middle of said two kinds of ink composites is said cyan ink composition; The content of the said green pigment in this cyan ink composition is 2.0 quality % to 4.0 quality % with respect to the total amount of said cyan ink composition, and said crosslinked water soluble resin and the mass ratio (quality of the quality/green pigment of crosslinked water soluble resin) of said green pigment are 0.40 or bigger; Perhaps
(3) when the ink composite that is at first sprayed in the middle of said two kinds of ink composites is said Yellow ink compsn; The content of the said yellow ultramarine in this Yellow ink compsn is 3.0 quality % to 6.0 quality % with respect to the total amount of said Yellow ink compsn, and said crosslinked water soluble resin and the mass ratio (quality of the quality/yellow ultramarine of crosslinked water soluble resin) of yellow ultramarine are 0.40 or bigger.
2. the described printing ink group of claim 1, the equal particle diameter of body that wherein is selected from least a resin-coated pigment in the group of being made up of said resin-coated yellow ultramarine, said resin-coated magenta pigment and said resin-coated green pigment is 50nm to 150nm.
3. the described printing ink group of claim 1, at least a ink composite that wherein is selected from the group of being made up of said Yellow ink compsn, said magenta ink compositions and said cyan ink composition further comprises Photoepolymerizationinitiater initiater.
4. the described printing ink group of claim 1, wherein at least a ink composite in being selected from the group of being made up of said Yellow ink compsn, said magenta ink compositions and said cyan ink composition, said water soluble resin comprises carboxyl.
5. the described printing ink group of claim 1; Wherein at least a resin-coated pigment in being selected from the group of forming by said resin-coated green pigment, said resin-coated magenta pigment and said resin-coated yellow ultramarine; Said water soluble resin comprises derived from the formation unit of (methyl) vinylformic acid benzyl ester with derived from (methyl) acrylic acid formation unit at least, and the acid number behind this water soluble resin crosslinked is 55mgKOH/g to 100mgKOH/g.
6. the described printing ink group of claim 1, the equal particle diameter of body that wherein is selected from least a resin-coated pigment in the group of being made up of said resin-coated green pigment and said resin-coated magenta pigment is 50nm to 100nm.
7. the described printing ink group of claim 1, the said agglutinant in the wherein said treatment solution is an acidic cpd.
8. the described printing ink group of claim 1; Wherein at least a ink composite in being selected from the group of forming by said Yellow ink compsn, said magenta ink compositions and said cyan ink composition; Said water-soluble polymerizable compound comprises that two or more are selected from the polymerizable functional group in the group of being made up of acrylamido, methacryloyl amido, dimaleoyl imino, ethene sulfuryl and N-vinylamide base, and the ratio of the number of the said polymerizable functional group that is contained in molecular weight and the molecule is 175 or littler.
9. use the formation method of any described printing ink group in the claim 1 to 8, this method comprises:
Treatment solution is applied on the recording medium, and wherein said treatment solution contains the composition agglutinative agglutinant that makes in the ink composite,
First ink composite that will be selected from said printing ink group through ink ejecting method is applied on the recording medium that has applied said treatment solution on it,
Second ink composite that will be selected from said printing ink group through ink ejecting method is applied on said first ink composite that is applied on the said recording medium, and
Through the active-energy radiation irradiation has been applied with on the recording medium of said ink composite on it, thereby said ink composite is solidified.
10. formation method according to claim 9, wherein said active-energy radiation are ultraviolet ray.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-024479 | 2011-02-07 | ||
| JP2011024479A JP5404669B2 (en) | 2011-02-07 | 2011-02-07 | Ink set and image forming method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102627885A true CN102627885A (en) | 2012-08-08 |
Family
ID=46586289
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012100202593A Pending CN102627885A (en) | 2011-02-07 | 2012-01-29 | Ink set and image forming method |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US8757786B2 (en) |
| JP (1) | JP5404669B2 (en) |
| CN (1) | CN102627885A (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2012162655A (en) | 2012-08-30 |
| US20120200651A1 (en) | 2012-08-09 |
| US8757786B2 (en) | 2014-06-24 |
| JP5404669B2 (en) | 2014-02-05 |
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